Material for forming organic film, method for forming organic film, patterning process, and compound

ABSTRACT

The present invention is a material for forming an organic film, including: a compound shown by the following general formula (1); and an organic solvent, where in the general formula (1), X represents an organic group with a valency of “n” having 2 to 50 carbon atoms or an oxygen atom, “n” represents an integer of 1 to 10, and R1 independently represents any of the following general formulae (2), where in the general formulae (2), broken lines represent attachment points to X, and Q1 represents a monovalent organic group containing a carbonyl group, at least a part of which is a group shown by the following general formulae (3), where in the general formulae (3), broken lines represent attachment points, X1 represents a single bond or a divalent organic group having 1 to 20 carbon atoms optionally having a substituent when the organic group has an aromatic ring, R2 represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and ** represents an attachment point. An object of the present invention is to provide a material for forming an organic film for forming an organic film having dry etching resistance, and also having high filling and planarizing properties and adhesion to a substrate.

TECHNICAL FIELD

The present invention relates to: a material for forming an organic filmfor forming a resist underlayer film used in a multilayer resist processor the like employed for fine processing in a manufacturing process of asemiconductor device, etc. and for forming an organic film effective asa planarizing material for manufacturing a semiconductor device, and thelike; a method for forming a film using this material; a patterningprocess suitable for exposure to deep ultraviolet ray, KrF excimer laserbeam (248 nm), ArF excimer laser beam (193 nm), F₂ laser beam (157 nm),Kr laser beam (146 nm), Ar laser beam (126 nm), soft X-ray (EUV),electron beam (EB), ion beam, X-ray, and the like using the material forforming an organic film; and a compound useful as a component of thematerial for forming an organic film.

BACKGROUND ART

As LSI advances toward high integration and high processing speed,miniaturization of pattern size is progressing rapidly. Along with theminiaturization, lithography technology has achieved a fine patterningby shortening the wavelength of a light source and selecting anappropriate resist composition accordingly. The composition mainly usedis a positive photoresist composition for monolayer. The monolayerpositive photoresist composition not only allows a resist resin to havea skeleton having etching resistance against dry etching with chlorine-or fluorine-based gas plasma, but also provides a resist mechanism thatmakes an exposed part soluble, thereby dissolving the exposed part toform a pattern and processing a substrate to be processed, on which theresist composition has been applied, by dry etching using the remainingresist pattern as an etching mask.

However, when the pattern becomes finer, that is, the pattern width isreduced without changing the thickness of the photoresist film to beused, resolution performance of the photoresist film is lowered. Inaddition, pattern development of the photoresist film with a developerexcessively increases a so-called aspect ratio of the pattern, resultingin pattern collapse. Therefore, the photoresist film has been thinnedalong with the miniaturization of the pattern.

On the other hand, a substrate to be processed has been generallyprocessed by dry etching while using a pattern-formed photoresist filmas an etching mask. In practice, however, there is no dry etching methodcapable of providing an absolute etching selectivity between thephotoresist film and the substrate to be processed. The resist film isthus damaged and collapses during processing of the substrate, and theresist pattern cannot be precisely transferred to the substrate to beprocessed. Accordingly, higher dry etching resistance has been requiredin a resist composition along with the miniaturization of the pattern.In addition, the use of shorter wavelength exposure radiations hasrequired resins used for photoresist compositions to have low absorbanceat the wavelength to be used for the exposure. Accordingly, as theradiation shifts from i-beam to KrF and to ArF, the resin shifts tonovolak resins, polyhydroxystyrene, and resins having an aliphaticpolycyclic skeleton. This shift actually accelerates an etching rateunder the above-described dry etching conditions, and recent photoresistcompositions having high resolution tend to have low etching resistance.

As a result, a substrate to be processed has to be dry etched with athinner photoresist film having lower etching resistance. The need toprovide a material for this process and the process itself has becomeurgent.

A multilayer resist method is one solution for these problems. Thismethod is as follows: a middle layer film having a different etchingselectivity from a photoresist film (i.e., a resist upper layer film) isplaced between the resist upper layer film and a substrate to beprocessed; a pattern is formed in the resist upper layer film; then, thepattern is transferred to the middle layer film by dry etching whileusing the resist upper layer film pattern as a dry etching mask; and thepattern is further transferred to the substrate to be processed by dryetching while using the middle layer film as a dry etching mask.

One of the multilayer resist methods is a 3-layer resist method, whichcan be performed with a typical resist composition used in the monolayerresist method. For example, this 3-layer resist method includes thefollowing steps: an organic film containing a novolak or the like isformed as a resist underlayer film on a substrate to be processed; asilicon-containing film is formed thereon as a resist middle layer film;a usual organic photoresist film is formed thereon as a resist upperlayer film. Since the organic resist upper layer film exhibits afavorable etching selectivity ratio relative to the silicon-containingresist middle layer film when dry etching is performed withfluorine-based gas plasma, the resist upper layer film pattern can betransferred to the silicon-containing resist middle layer film byemploying dry etching with fluorine-based gas plasma. Furthermore, sincethe silicon-containing resist middle layer film exhibits a favorableetching selectivity ratio relative to an organic underlayer film in theetching using an oxygen gas or a hydrogen gas, a silicon-containingmiddle layer film pattern is transferred to the underlayer film by meansof etching using an oxygen gas or a hydrogen gas. According to thisprocess, even when a resist composition which is difficult to form apattern in so that the pattern has a sufficient film thickness fordirectly processing the substrate to be processed or a resistcomposition which has insufficient dry etching resistance for processingthe substrate is used, a pattern of an organic film (resist underlayerfilm) containing a novolak or the like having a sufficient dry etchingresistance for the processing can be obtained when the pattern can betransferred to the silicon-containing film (resist middle layer film).

While numerous processes have been known (for example, PatentDocument 1) for the organic underlayer film as described above, inrecent years, there has now been growing necessity to have excellentfilling property, planarizing property and adhesiveness to a substratein addition to dry etching resistance. For example, when an underlyingsubstrate to be processed has a fine pattern structure such as a hole ora trench, it is necessary to have filling property for filling in thepattern with a film without any voids. In addition, when the underlyingsubstrate to be processed has a step(s), or when a pattern-dense regionand a pattern-free region exist on the same substrate, it is necessaryto planarize the film surface by the underlayer film. By planarizing thesurface of the underlayer film, fluctuation in the film thickness of amiddle layer or a photoresist formed thereon is controlled, whereby afocus margin in lithography or a margin in the processing step of thesubstrate to be processed thereafter can be enlarged. Furthermore, whenan inorganic hard mask is formed on the organic underlayer film,adhesion to a substrate is necessary. When adhesion is enhanced, filmdelamination on forming an inorganic hard mask directly on an organicfilm by a CVD method or an ALD method can be prevented, and an organicfilm excellent in process margin can be formed.

To improve the filling and planarizing properties of an underlayer filmmaterial, addition of a liquid additive such as polyether polyol hasbeen proposed (Patent Document 2). However, an organic film formed bythis method contains many polyether polyol units, which are inferior inetching resistance. Thus, this film has a markedly lowered etchingresistance and is unsuitable for the 3-layer resist underlayer film. Inaddition, a resist underlayer film material having a lactone ringstructure as a component has been suggested as a means for enhancing theadhesion of the underlayer film material to a substrate (Patent Document3). However, the resist underlayer film material has a problem that theadhesiveness to a substrate is not sufficient for the requirements in acutting-edge device. Accordingly, a resist underlayer film materialhaving excellent filling and planarizing properties and adhesion to asubstrate as well as sufficient etching resistance, and a patterningprocess using this material are desired.

Moreover, the organic film material excellent in filling property,planarizing property, and adhesion to a substrate is not limited to usefor the underlayer film for 3-layer resist, and is widely usable also asa planarizing material for manufacturing a semiconductor device, e.g.,for planarizing a substrate prior to patterning by nanoimprinting. Forglobal planarizing in the semiconductor device manufacturing process, aCMP process is now generally used. However, the CMP process is costly,so that this material is also expected to be used for the globalplanarizing method, instead of CMP.

CITATION LIST Patent Literature Patent Document 1: JP 2004-205685 APatent Document 2: JP 4784784 B Patent Document 3: JP 3985165 B SUMMARYOF INVENTION Technical Problem

The present invention has been accomplished in view of the abovecircumstances, and an object thereof is to provide a material forforming an organic film for forming an organic film having dry etchingresistance, and also having high filling and planarizing properties andadhesion to a substrate.

Solution to Problem

To achieve the object, the present invention provides a material forforming an organic film, comprising: a compound shown by the followinggeneral formula (1); and an organic solvent,

wherein in the general formula (1), X represents an organic group with avalency of “n” having 2 to 50 carbon atoms or an oxygen atom, “n”represents an integer of 1 to 10, and R₁ independently represents any ofthe following general formulae (2),

wherein in the general formulae (2), broken lines represent attachmentpoints to X, and Q₁ represents a monovalent organic group containing acarbonyl group, at least a part of which is a group shown by thefollowing general formulae (3),

wherein in the general formulae (3), broken lines represent attachmentpoints, X₁ represents a single bond or a divalent organic group having 1to 20 carbon atoms optionally having a substituent when the organicgroup has an aromatic ring, R₂ represents a hydrogen atom, a methylgroup, an ethyl group, or a phenyl group, and ** represents anattachment point.

An organic film having high dry etching resistance as well as highfilling and planarizing properties can be formed with such a materialfor forming an organic film. Furthermore, adhesiveness to a substrate ishigh since the compound has two carbonyl groups, and when the compoundalso has an amide group, an organic film having higher adhesiveness canbe formed.

In this event, the compound shown by the general formula (1) in thematerial for forming an organic film is preferably shown by thefollowing general formulae (4), (6), (7), (8), (9), (10), (11), (12),(13), and (14),

wherein in the general formula (4), n7 and n8 each independentlyrepresent 0 or 1, W represents a single bond or any structure shown bythe following general formulae (5), R₁ has the same meaning as definedabove, m1 and m2 each independently represent an integer of 0 to 4, andm1+m2 is 1 or more to 8 or less,

wherein in the general formulae (5), n9 represents an integer of 0 to 3,R_(a) to R_(f) each independently represent a hydrogen atom or anoptionally fluorine-substituted alkyl group having 1 to 10 carbon atomsor phenyl group, and R_(a) and R_(b) are optionally bonded with eachother to form a ring,

wherein in the general formula (6), R_(g) represents a hydrogen atom, amethyl group, or a phenyl group.

In the general formulae (7) to (11), R₁ has the same meaning as definedabove, R_(h), R_(i), R_(j), R_(k), R_(l), R_(m), and R_(n) eachrepresent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2to 10 carbon atoms, or a benzyl group or a phenyl group optionallyhaving a substituent on an aromatic ring, Y represents R₁, a hydrogenatom, an alkyl group having 1 to 10 carbon atoms, an alkynyl grouphaving 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbonatoms, and at least two of the four Ys in the general formula (11)represent R₁.

In the general formulae (12) to (14), R₁ has the same meaning as definedabove, R_(o) in the general formula (12) represents a linear saturatedor unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms ora branched or cyclic saturated or unsaturated divalent hydrocarbon grouphaving 3 to 20 carbon atoms, and R_(p) in the general formula (13)represents a hydrogen atom or an alkyl group having 1 to 10 carbonatoms.

Such a material for forming an organic film can provide an organic filmhaving favorable dry etching resistance as well as high fillingproperty, planarizing property, and adhesiveness to a substrate.

Furthermore, the present invention provides a material for forming anorganic film, wherein Q₁ in the general formula (2) comprises any one ormore shown by the general formulae (3) and any one or more shown by thefollowing general formulae (15) and (16),

wherein R_(q) in the general formula (15) represents a linear saturatedor unsaturated hydrocarbon group having 1 to 30 carbon atoms or abranched or cyclic saturated or unsaturated hydrocarbon group having 3to 30 carbon atoms, a methylene group comprised in R_(q) is optionallysubstituted with an oxygen atom or a carbonyl group, and in the generalformula (16), R_(s) represents a hydrogen atom, a linear hydrocarbongroup having 1 to 10 carbon atoms, or a branched hydrocarbon grouphaving 3 to 10 carbon atoms, R_(t) represents a linear hydrocarbon grouphaving 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10carbon atoms, a halogen atom, a nitro group, an amino group, a nitrilegroup, an alkoxycarbonyl group having 1 to 10 carbon atoms, or analkanoyloxy group having 1 to 10 carbon atoms, n11 represents 0 to 2,n12 and n13 represent a number of substituents on the aromatic ring, n12and n13 represent an integer of 0 to 7, and n12+n13 is 0 or more to 7 orless.

When the material for forming an organic film contains such a compound,various physical properties such as heat resistance, etching resistance,high filling and planarizing properties, adhesiveness to a substrate,and control of an optical constant can be appropriately adjusted andimproved according to the required performance by combining an aromaticring structure and a structure of a hydrocarbon terminal group.

Furthermore, the organic solvent is preferably a mixture of one or moreorganic solvents each having a boiling point of lower than 180° C. andone or more organic solvents each having a boiling point of 180° C. orhigher.

With such a material for forming an organic film, the above-describedpolymer is provided with thermal flowability of films by adding ahigh-boiling-point solvent, so that a material for forming an organicfilm having both high filling and planarizing properties is achieved.

In this manner, when the inventive material for forming an organic filmis used, for example, for forming a multilayer resist film applied infine processing in a manufacturing process of a semiconductor device,etc., an organic film (resist underlayer film) having high dry etchingresistance as well as high filling and planarizing properties andadhesion to a substrate can be provided. In addition, a planarizingmaterial for manufacturing a semiconductor device that can be appliedfor planarizing in a semiconductor device manufacturing process otherthan a multilayer resist process and that has high filling andplanarizing properties and adhesion to a substrate can also be provided.

Furthermore, the present invention provides a method for forming anorganic film that functions as an organic flat film employed in asemiconductor device manufacturing process, the method comprising:

spin-coating a substrate to be processed with the material for formingan organic film; and

heating the substrate to be processed at a temperature of 100° C. orhigher to 600° C. or lower for 10 to 600 seconds to form a cured film.

In this manner, by coating with the material for forming an organic filmand heating the material for forming an organic film at a temperature of100° C. or higher to 600° C. or lower for 10 to 600 seconds,crosslinking reaction is promoted, and mixing with the upper layer filmcan be prevented.

Furthermore, the present invention provides a method for forming anorganic film that functions as an organic flat film employed in asemiconductor device manufacturing process, the method comprising:

spin-coating a substrate to be processed with the material for formingan organic film; and

heating the substrate to be processed in an atmosphere having an oxygenconcentration of 0.1% or more to 21% or less to form a cured film.

When the inventive material for forming an organic film is heated(baked) in such an oxygen atmosphere, a sufficiently cured organic filmcan be obtained.

In the above, the substrate to be processed preferably has a structureor a step with a height of 30 nm or more.

The inventive material for forming an organic film is excellent in highfilling and planarizing properties and adhesion to a substrate, and istherefore, particularly useful when forming a flat organic film on asubstrate having a structure or a step with a height of 30 nm or more.

Furthermore, the present invention provides a patterning processcomprising:

forming a resist underlayer film by using the material for forming anorganic film on a body to be processed;

forming a resist middle layer film by using a resist middle layer filmmaterial containing a silicon atom on the resist underlayer film;

forming a resist upper layer film by using a resist upper layer filmmaterial being a photoresist composition on the resist middle layerfilm;

forming a circuit pattern in the resist upper layer film;

transferring the pattern to the resist middle layer film by etchingwhile using the resist upper layer film having the formed circuitpattern as an etching mask;

transferring the pattern to the resist underlayer film by etching whileusing the resist middle layer film having the transferred circuitpattern as an etching mask; and

further forming the circuit pattern on the body to be processed byetching while using the resist underlayer film having the transferredcircuit pattern as an etching mask.

In such a multilayer resist process, a fine pattern can be formed withhigh precision on a substrate to be processed according to thepatterning process using the inventive material for forming an organicfilm.

Furthermore, the present invention provides a patterning processcomprising:

forming a resist underlayer film by using the material for forming anorganic film on a body to be processed;

forming a resist middle layer film by using a resist middle layer filmmaterial containing a silicon atom on the resist underlayer film;

forming a BARC (organic antireflective coating) on the resist middlelayer film;

forming a resist upper layer film by using a resist upper layer filmmaterial being a photoresist composition on the BARC so that a 4-layeredfilm structure is constructed;

forming a circuit pattern in the resist upper layer film;

transferring the pattern to the BARC and the resist middle layer film byetching while using the resist upper layer film having the formedcircuit pattern as an etching mask;

transferring the pattern to the resist underlayer film by etching whileusing the resist middle layer film having the transferred circuitpattern as an etching mask; and

further forming the circuit pattern on the body to be processed byetching while using the resist underlayer film having the transferredcircuit pattern as an etching mask.

As described, instead of forming a photoresist film directly on theresist middle layer film as a resist upper layer film, a BARC (organicantireflective coating) can be formed on the resist middle layer film byspin-coating or the like, and the resist upper layer film can be formedthereon.

Furthermore, the present invention provides a patterning processcomprising:

forming a resist underlayer film by using the material for forming anorganic film on a body to be processed;

forming an inorganic hard mask middle layer film selected from a siliconoxide film, a silicon nitride film, and a silicon oxynitride film on theresist underlayer film;

forming a resist upper layer film by using a resist upper layer filmmaterial being a photoresist composition on the inorganic hard maskmiddle layer film;

forming a circuit pattern in the resist upper layer film;

transferring the pattern to the inorganic hard mask middle layer film byetching while using the resist upper layer film having the formedcircuit pattern as an etching mask;

transferring the pattern to the resist underlayer film by etching whileusing the inorganic hard mask middle layer film having the transferredcircuit pattern as an etching mask; and

further forming the circuit pattern on the body to be processed byetching while using the resist underlayer film having the transferredcircuit pattern as an etching mask.

Furthermore, the present invention provides a patterning processcomprising:

forming a resist underlayer film by using the material for forming anorganic film on a body to be processed;

forming an inorganic hard mask middle layer film selected from a siliconoxide film, a silicon nitride film, and a silicon oxynitride film on theresist underlayer film;

forming a BARC (organic antireflective coating) on the inorganic hardmask middle layer film;

forming a resist upper layer film by using a resist upper layer filmmaterial being a photoresist composition on the BARC, so that a4-layered film structure is constructed;

forming a circuit pattern in the resist upper layer film;

transferring the pattern to the BARC and the inorganic hard mask middlelayer film by etching while using the resist upper layer film having theformed circuit pattern as an etching mask;

transferring the pattern to the resist underlayer film by etching whileusing the inorganic hard mask middle layer film having the transferredcircuit pattern as an etching mask; and

further forming the circuit pattern on the body to be processed byetching while using the resist underlayer film having the transferredcircuit pattern as an etching mask.

As described, the resist middle layer film may be formed on the resistunderlayer film, but instead, any inorganic hard mask middle layer filmselected from a silicon oxide film, a silicon nitride film, and asilicon oxynitride film can also be formed on the resist underlayerfilm. Furthermore, a photoresist film may be formed directly on theinorganic hard mask middle layer film as a resist upper layer film, butalternatively, a BARC (organic antireflective coating) can be formed onthe inorganic hard mask middle layer film by spin-coating or the like,and the resist upper layer film can be formed thereon. When a SiON film(silicon oxynitride film) is used as the inorganic hard mask middlelayer film, the two layers of antireflective coating including the SiONfilm and the BARC make it possible to suppress the reflection even inliquid immersion exposure at a high NA exceeding 1.0. Another advantagein forming the BARC is having an effect of reducing footing of thephotoresist pattern immediately above the SiON film.

In addition, in the inventive patterning process, the inorganic hardmask middle layer film can be formed by a CVD method or an ALD method.

As described, in the inventive patterning process, an inorganic hardmask middle layer film formed by a CVD method or an ALD method and aresist underlayer film formed by a spin-coating method or the like canbe combined.

Furthermore, in the pattern formation on the resist upper layer film,the pattern is preferably formed by a photolithography with a wavelengthof 10 nm or more to 300 nm or less, a direct drawing by electron beam, ananoimprinting, or a combination thereof.

In addition, development in the patterning process is preferablyalkaline development or development with an organic solvent.

Such a patterning process and development method can be suitably used inthe present invention.

Furthermore, the body to be processed is preferably a semiconductordevice substrate or the semiconductor device substrate coated with anyof a metal film, a metal carbide film, a metal oxide film, a metalnitride film, a metal oxycarbide film, or a metal oxynitride film.

Furthermore, as the body to be processed, a body to be processedincluding metallic silicon, titanium, tungsten, hafnium, zirconium,chromium, germanium, copper, silver, gold, aluminum, indium, gallium,arsenic, palladium, iron, tantalum, iridium, cobalt, manganese,molybdenum, or an alloy thereof is preferably used.

According to the inventive patterning process, the above-described bodyto be processed can be used to process and to form a pattern.

Moreover, the present invention provides a compound shown by thefollowing general formula (1),

wherein in the general formula (1), X represents an organic group with avalency of “n” having 2 to 50 carbon atoms or an oxygen atom, “n”represents an integer of 1 to 10, and R₁ independently represents any ofthe following general formulae (2),

wherein in the general formulae (2), broken lines represent attachmentpoints to X, and Q₁ represents a monovalent organic group containing acarbonyl group, at least a part of which is a group shown by thefollowing general formulae (3),

wherein in the general formulae (3), broken lines represent attachmentpoints, X₁ represents a single bond or a divalent organic group having 1to 20 carbon atoms optionally having a substituent when the organicgroup has an aromatic ring, R₂ represents a hydrogen atom, a methylgroup, an ethyl group, or a phenyl group, and ** represents anattachment point.

When the inventive compound is used as a component in a material forforming an organic film, an organic film having high dry etchingresistance as well as high filling and planarizing properties can beformed with the obtained material for forming an organic film. Highthermosetting property can be provided by appropriately selecting aterminal substituent containing a triple bond, and film shrinking duringbaking can be reduced. When film shrinking is reduced, an organic filmexcellent in planarizing property can be formed, and in addition, theinternal stress of the coating film is reduced, so that adhesiveness toa substrate is also enhanced. Furthermore, the adhesiveness to asubstrate is high since the terminal substituent has two carbonylgroups, and when an amide group is also contained, an organic filmhaving higher adhesiveness can be formed. In addition, since thecompound has a terminal substituent containing a triple bond, sufficientthermosetting property is exhibited without generating a sublimationproduct even under an inert gas atmosphere. Therefore, a film can beformed without damage to a carbonyl group or an amide group, and highadhesiveness to a substrate is exhibited not only in the atmosphere, butalso under inert gas. Consequently, the inventive compound is extremelyuseful for a material for forming an organic film for forming an organicfilm excellent in high filling property, high planarizing property, andadhesiveness to a substrate.

In this event, the compound shown by the general formula (1) ispreferably any of the compounds shown by the following general formulae(4), (6), (7), (8), (9), (10), (11), (12), (13), and (14),

wherein in the general formula (4), n7 and n8 each independentlyrepresent 0 or 1, W represents a single bond or any structure shown bythe following general formulae (5), R₁ has the same meaning as definedabove, m1 and m2 each independently represent an integer of 0 to 4, andm1+m2 is 1 or more to 8 or less,

wherein in the general formulae (5), n9 represents an integer of 0 to 3,R_(a) to R_(f) each independently represent a hydrogen atom or anoptionally fluorine-substituted alkyl group having 1 to 10 carbon atomsor phenyl group, and R_(a) and R_(b) are optionally bonded with eachother to form a ring,

wherein in the general formula (6), R_(g) represents a hydrogen atom, amethyl group, or a phenyl group.

In the general formulae (7) to (11), R₁ has the same meaning as definedabove, R_(h), R_(i), R_(j), R_(k), R_(l), R_(m), and R_(n) eachrepresent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2to 10 carbon atoms, or a benzyl group or a phenyl group optionallyhaving a substituent on an aromatic ring, Y represents R₁, a hydrogenatom, an alkyl group having 1 to 10 carbon atoms, an alkynyl grouphaving 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbonatoms, and at least two of the four Ys in the general formula (11)represent R₁.

In the general formulae (12) to (14), R₁ has the same meaning as definedabove, R_(o) in the general formula (12) represents a linear saturatedor unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms ora branched or cyclic saturated or unsaturated divalent hydrocarbon grouphaving 3 to 20 carbon atoms, and R_(p) in the general formula (13)represents a hydrogen atom or an alkyl group having 1 to 10 carbonatoms.

Such a compound is excellent in high filling property, planarizingproperty, and adhesiveness, and etching resistance and opticalcharacteristics can be appropriately adjusted according to the requiredperformance. When the compound is used as a component of a material forforming an organic film, the material for forming an organic film canform an organic film having both dry etching resistance and adhesivenessto a substrate according to the required performance.

In this event, the compound can be such that Q₁ in the general formula(2) comprises any one or more shown by the general formulae (3) and anyone or more shown by the following general formulae (15) and (16),

wherein R_(q) in the general formula (15) represents a linear saturatedor unsaturated hydrocarbon group having 1 to 30 carbon atoms or abranched or cyclic saturated or unsaturated hydrocarbon group having 3to 30 carbon atoms, a methylene group comprised in R_(q) is optionallysubstituted with an oxygen atom or a carbonyl group, and in the generalformula (16), R_(s) represents a hydrogen atom, a linear hydrocarbongroup having 1 to 10 carbon atoms, or a branched hydrocarbon grouphaving 3 to 10 carbon atoms, R_(t) represents a linear hydrocarbon grouphaving 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10carbon atoms, a halogen atom, a nitro group, an amino group, a nitrilegroup, an alkoxycarbonyl group having 1 to 10 carbon atoms, or analkanoyloxy group having 1 to 10 carbon atoms, n11 represents 0 to 2,n12 and n13 represent a number of substituents on the aromatic ring, n12and n13 represent an integer of 0 to 7, and n12+n13 is 0 or more to 7 orless.

When such a compound is blended in a material for forming an organicfilm, an aromatic ring structure and a structure of a hydrocarbonterminal group are combined so that when the compound is used as acomponent in a material for forming an organic film, various physicalproperties such as heat resistance, etching resistance, high filling andplanarizing properties, adhesiveness to a substrate, and control of anoptical constant can be appropriately adjusted and improved according tothe required performance.

Advantageous Effects of Invention

As described above, the present invention can provide: a compound usefulas a component of a material for forming an organic film for forming anorganic film having high filling and planarizing properties and adhesionto a substrate; and a material for forming an organic film containingthe compound. Moreover, this material for forming an organic film hashigh filling and planarizing properties and adhesion to a substrate, andis also a material for forming an organic film provided with othercharacteristics such as heat resistance and etching resistance.Accordingly, the material for forming an organic film is extremelyuseful as a resist underlayer film material in a multilayer resistprocess such as a 2-layer resist process, a 3-layer resist process usinga middle layer film containing a silicon atom, or a 4-layer resistprocess using a middle layer film containing a silicon atom and anorganic antireflective coating, or as a planarizing material formanufacturing a semiconductor device, for example.

In addition, according to the inventive method for forming an organicfilm, a sufficiently cured and flat organic film can be formed on asubstrate to be processed. Furthermore, according to the inventivepatterning process, a fine pattern can be formed with high precision ona substrate to be processed in a multilayer resist process.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an explanatory diagram of an example of an inventivepatterning process according to a 3-layer resist process.

FIG. 2 is an explanatory diagram of a method for evaluating the fillingproperty in Examples and Comparative Examples.

FIG. 3 is an explanatory diagram of a method for evaluating theplanarizing property in Examples and Comparative Examples.

FIG. 4 is an explanatory diagram showing a method for measuring theadhesiveness in Examples.

DESCRIPTION OF EMBODIMENTS

As described above, a material for forming an organic film for formingan organic film having high filling and planarizing properties andadhesion to a substrate has been desired.

The present inventors have earnestly studied the above problems andfound out that a material for forming an organic film containing acompound shown by the following general formula (1) can form an organicfilm having high filling and planarizing properties and excellentadhesion to a substrate, and thus completed the present invention.

That is, the present invention is a material for forming an organicfilm, containing: a compound shown by the following general formula (1);and an organic solvent,

where in the general formula (1), X represents an organic group with avalency of “n” having 2 to 50 carbon atoms or an oxygen atom, “n”represents an integer of 1 to 10, and R₁ independently represents any ofthe following general formulae (2),

where in the general formulae (2), broken lines represent attachmentpoints to X, and Q₁ represents a monovalent organic group containing acarbonyl group, at least a part of which is a group shown by thefollowing general formulae (3),

where in the general formulae (3), broken lines represent attachmentpoints, X₁ represents a single bond or a divalent organic group having 1to 20 carbon atoms optionally having a substituent when the organicgroup has an aromatic ring, R₂ represents a hydrogen atom, a methylgroup, an ethyl group, or a phenyl group, and ** represents anattachment point.

Hereinafter, embodiments of the present invention will be described, butthe present invention is not limited thereto. Note that the inventivematerial for forming an organic film is sometimes referred to as anorganic film material or a composition for forming an organic film,hereinafter.

[Compound for Forming Organic Film]

The inventive compound is shown by the following general formula (1),

where in the general formula (1), X represents an organic group with avalency of “n” having 2 to 50 carbon atoms or an oxygen atom, “n”represents an integer of 1 to 10, and R₁ independently represents any ofthe following general formulae (2),

where in the general formulae (2), broken lines represent attachmentpoints to X, and Q₁ represents a monovalent organic group containing acarbonyl group, at least a part of which is a group shown by thefollowing general formulae (3),

where in the general formulae (3), broken lines represent attachmentpoints, X₁ represents a single bond or a divalent organic group having 1to 20 carbon atoms optionally having a substituent when the organicgroup has an aromatic ring, R₂ represents a hydrogen atom, a methylgroup, an ethyl group, or a phenyl group, and ** represents anattachment point.

Specific examples of the compound shown by the general formula (1)include the following (parts excluding R₁ are X). In the followingformulae, R₁ has the same meaning as defined above. m1 and m2 eachindependently represent an integer of 0 to 4, and m1+m2 is 1 or more to8 or less. n9 represents an integer of 0 to 3. Here, R₁ eachindependently represents any of the general formulae (2), and all theR₁s may be the same.

Furthermore, specific examples of X₁ in the general formulae (3) includethe following.

(The broken lines represent attachment points.)

In this event, the compound of the general formula (1) is preferably acompound shown by the following general formulae (4), (6), (7), (8),(9), (10), (11), (12), (13), and (14).

(In the general formula (4), n7 and n8 each independently represent 0 or1, and W represents a single bond or any structure shown by thefollowing (5). R₁ has the same meaning as defined above, m1 and m2 eachindependently represent an integer of 0 to 4, and m1+m2 is 1 or more to8 or less.)

(In the general formulae (5), n9 represents an integer of 0 to 3, R_(a)to R_(f) each independently represent a hydrogen atom or an optionallyfluorine-substituted alkyl group having 1 to 10 carbon atoms or phenylgroup, and R_(a) and R_(b) are optionally bonded with each other to forma ring.)

(In the general formula (6), R_(g) represents a hydrogen atom, a methylgroup, or a phenyl group.)

(In the general formulae (7) to (11), R₁ has the same meaning as definedabove, R_(h), R_(i), R_(j), R_(k), R_(l), R_(m), and R_(n) eachrepresent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2to 10 carbon atoms, or a benzyl group or a phenyl group optionallyhaving a substituent on an aromatic ring. Y represents R₁, a hydrogenatom, an alkyl group having 1 to 10 carbon atoms, an alkynyl grouphaving 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbonatoms, and at least two of the four Ys in the general formula (11)represent R₁.)

(In the general formulae (12) to (14), R₁ has the same meaning asdefined above, R_(o) in the general formula (12) represents a linearsaturated or unsaturated divalent hydrocarbon group having 1 to 20carbon atoms or a branched or cyclic saturated or unsaturated divalenthydrocarbon group having 3 to 20 carbon atoms, and R_(p) in the generalformula (13) represents a hydrogen atom or an alkyl group having 1 to 10carbon atoms.)

As the compound shown by the general formula (4), the following areparticularly favorable from the viewpoints of heat resistance andetching resistance.

As the compound shown by the general formula (6), the following areparticularly favorable from the viewpoints of heat resistance, etchingresistance, and curability.

In the present invention, the following are particularly favorable amongthe compounds shown by the general formulae (7) to (11) from theviewpoints of etching resistance, optical characteristics, andadhesiveness.

In the present invention, the following are particularly favorable amongthe compounds shown by the general formulae (12) to (14) from theviewpoints of high filling property, planarizing, and adhesiveness.

In addition, Q₁ in the general formula (2) can include any one or moreshown by the general formulae (3) and any one or more shown by thefollowing general formulae (15) and (16).

(R_(q) in the general formula (15) represents a linear saturated orunsaturated hydrocarbon group having 1 to 30 carbon atoms or a branchedor cyclic saturated or unsaturated hydrocarbon group having 3 to 30carbon atoms, and a methylene group included in R_(q) is optionallysubstituted with an oxygen atom or a carbonyl group. In the generalformula (16), R_(s) represents a hydrogen atom, a linear hydrocarbongroup having 1 to 10 carbon atoms, or a branched hydrocarbon grouphaving 3 to 10 carbon atoms, and R_(t) represents a linear hydrocarbongroup having 1 to 10 carbon atoms, a branched hydrocarbon group having 3to 10 carbon atoms, a halogen atom, a nitro group, an amino group, anitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, oran alkanoyloxy group having 1 to 10 carbon atoms. n11 represents 0 to 2,n12 and n13 represent a number of substituents on the aromatic ring, n12and n13 represent an integer of 0 to 7, and n12+n13 is 0 or more to 7 orless.)

Examples of the terminal group structure shown by the general formula(15) include the following. In the following formulae, n14 represents aninteger of 0 to 30, and n15 represents an integer of 0 to 20.

Examples of the terminal group structure shown by the general formula(16) include the following. n16 in the following formulae represent aninteger of 0 to 9.

A material for forming an organic film containing these compounds makesit possible to adjust various physical properties such as heatresistance, etching resistance, high filling and planarizing properties,and adhesion to a substrate according to the required performance bycombining the terminal group structures. In addition, since an opticalconstant can also be controlled, it becomes possible to provide anappropriate optical constant particularly at the time of exposure inmultilayer ArF lithography, and reflected light can be suppressed sothat an excellent resolution can be achieved.

In addition, when a material for forming an organic film containing sucha compound is used as a resist underlayer film material used for forminga multilayer resist film applied in fine processing in a manufacturingprocess of a semiconductor device, etc., a resist underlayer filmmaterial for forming a resist underlayer film having high filling andplanarizing properties and adhesion to a substrate, a method for forminga resist underlayer film, and a patterning process can be provided. Inaddition, in the present invention, a planarizing material formanufacturing a semiconductor device that can be applied for planarizingin a semiconductor device manufacturing process other than a multilayerresist process and that has high filling and planarizing properties andadhesion to a substrate can also be provided.

[Method for Manufacturing Compound]

The compound (compound for an organic film material) used in theinventive material for forming an organic film can be manufactured byselecting the optimum method according to the structure of the compound.Hereinafter, an example of a method for synthesizing the compound for anorganic film material shown by the general formula (1) will be describedin detail. Note that the method for manufacturing a compound for anorganic film material is not limited thereto.

Specific examples of the manufacturing method include a methodincluding: a first step of obtaining a carboxylic acid compound shown byany of the following general formulae (17) by an addition reactionbetween a carboxylic acid anhydride shown by (X₁CO)₂O and an alcohol oran amine; and

(in the general formulae (17), X₁ and R₂ have the same meanings asdefined above)

a second step of obtaining a compound for an organic film material shownby the general formula (1) by an addition reaction between an epoxycompound shown by the following general formula (18) and a carboxylicacid compound (monocarboxylic acid) shown by the general formulae (17).

(In the general formula (18), X and “n” have the same meanings asdefined above, and R₃ represents any of the following general formulae(19).)

(In the general formulae (19), the broken lines represent attachmentpoints to X.)

In the reaction between the carboxylic acid anhydride and the alcohol orthe amine in the first step, the used amount of the alcohol or the amineis preferably 0.5 to 1.5 mol, more preferably 0.7 to 1.3 mol, andfurther preferably 0.8 to 1.2 mol per 1 mol of the carboxylic acidanhydride.

The first step can be performed by mixing the raw materials in a solventor without a solvent by cooling or heating. When a solvent is used inthe reaction, specific examples of the solvent include: alcohols such asmethanol, ethanol, isopropyl alcohol, butanol, ethylene glycol,propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethylcellosolve, butyl cellosolve, and propyleneglycolmonomethyl ether;ethers such as diethyl ether, dibutyl ether, diethyleneglycoldiethylether, diethyleneglycoldimethyl ether, tetrahydrofuran, and 1,4-dioxane;chlorinated solvents such as methylene chloride, chloroform,dichloroethane, and trichloroethylene; hydrocarbons such as hexane,heptane, benzene, toluene, xylene, and cumene; nitriles such asacetonitrile; ketones such as acetone, ethylmethyl ketone, andisobutylmethyl ketone; esters such as ethyl acetate, n-butyl acetate,and propyleneglycolmethyl ether acetate; lactones such asγ-butyrolactone; and non-protic polar solvents such asdimethylsulfoxide, N,N-dimethylformamide, and hexamethylphosphorictriamide. These can be used alone or in mixture of two or more thereof.These solvents can be used within a range of 0 to 2,000 parts by massbased on 100 parts by mass of the starting material.

For these syntheses, a base catalyst can be used as necessary, andexamples of the base catalyst include: inorganic base compounds such assodium hydrogen carbonate, sodium carbonate, potassium carbonate,calcium carbonate, cesium carbonate, sodium hydroxide, potassiumhydroxide, sodium hydride, and potassium phosphate; organic bases suchas triethyl amine, diisopropyl ethyl amine, N,N-dimethylaniline,pyridine, and 4-dimethylaminopyridine; and the like. These can be usedalone or in combination of two or more thereof. The amount of thecatalyst used is preferably within the range of 0.001 to 100 mass %based on the total amount of the starting material, more preferably0.005 to 50 mass %.

The reaction temperature is preferably −20° C. to 200° C., morepreferably 0° C. to 150° C. When a solvent is used, it is preferable toset the upper limit of the reaction temperature to approximately theboiling point of the solvent. When the reaction temperature is −20° C.or higher, there is no risk of the reaction being slowed down, and whenthe reaction temperature is 200° C. or lower, side reactions such as adecomposition reaction of a product do not easily occur. The reactiontime of the above reaction is usually about 0.5 to 200 hours, and it ispreferable to determine the reaction time by tracing the progress of thereaction by thin-layer chromatography, liquid chromatography, gelfiltration chromatography, or the like to improve the yield. Aftercompletion of the reaction, a usual aqueous post-treatment (aqueouswork-up) can be performed as necessary to obtain the compound shown bythe formulae (17). The compound shown by the formulae (17) can berefined by a usual method such as crystallization, liquid separation,chromatography, and adsorption treatment according to the properties ofthe compound if necessary. In some cases, it is also possible to proceeddirectly to the second step without any additional treatments after thereaction.

As methods for performing the reaction, for example, it is possible toadopt a method of charging the raw materials, reaction catalyst, and ifnecessary, a solvent at once, or a method of adding the raw materials orraw material solution dropwise alone or in mixture in the presence of areaction catalyst.

In the reaction between the epoxy compound and the carboxylic acidcompound in the second step, the used amount of the carboxylic acid ispreferably 0.3 to 2.0 mol, more preferably 0.5 to 1.5 mol, and furtherpreferably 0.75 to 1.25 mol per 1 mol of the epoxy in the epoxycompound. When the used amount of the carboxylic acid is appropriaterelative to the epoxy unit as described, there is no risk of unreactedepoxy group remaining and degrading the storage stability of the organicfilm material, and it is possible to prevent unreacted carboxylic acidfrom remaining and causing outgassing.

Additionally, in the reaction between the epoxy compound and thecarboxylic acid compound, a plurality of carboxylic acid compounds canalso be used at the same time within the range of the used amount of thecarboxylic acid to improve the required performance such as opticalconstant (n/k), thermal flowability, etching resistance, heatresistance, solvent solubility, and adhesion to a substrate. As such acombination of carboxylic acid compounds, the carboxylic acid compoundsshown by any of the general formulae (17) can be combined, and it isparticularly preferable to combine a carboxylic acid compound(carboxylic acid compound (20)) shown by the following general formula(20) and a carboxylic acid compound (carboxylic acid compound (21))shown by the following general formula (21) at the same time. It is alsopossible to combine a plurality of carboxylic acid compounds (20) andcarboxylic acid compounds (21) at the same time. The used amount of thecarboxylic acid compound (20) and the carboxylic acid compound (21) whenused at the same time can each be adjusted within the range of 1 to 99mol % when the total amount of used carboxylic acid is set to 100 mol %.20 mol % or more of the carboxylic acid compound (21) is preferablyused, more preferably 30 mol % or more from the viewpoints of etchingresistance and heat resistance.

(In the formula, R_(q) has the same meaning as defined above.)

(In the formula, R_(s), R_(t), n11, n12, and n13 have the same meaningsas defined above.)

The above-described compound can usually be obtained by allowing anepoxy compound and a carboxylic acid compound to react, without asolvent or in a solvent in the presence of a reaction catalyst in roomtemperature or under cooling or heating as necessary. When a solvent isused in the reaction, specific examples of the solvent to be usedinclude: alcohols such as methanol, ethanol, isopropyl alcohol, butanol,ethylene glycol, propylene glycol, diethylene glycol, glycerol, methylcellosolve, ethyl cellosolve, butyl cellosolve, andpropyleneglycolmonomethyl ether; ethers such as diethyl ether, dibutylether, diethyleneglycoldiethyl ether, diethyleneglycoldimethyl ether,tetrahydrofuran, and 1,4-dioxane; chlorinated solvents such as methylenechloride, chloroform, dichloroethane, and trichloroethylene;hydrocarbons such as hexane, heptane, benzene, toluene, xylene, andcumene; nitriles such as acetonitrile; ketones such as acetone,ethylmethyl ketone, and isobutylmethyl ketone; esters such as ethylacetate, n-butyl acetate, and propyleneglycolmethyl ether acetate;lactones such as γ-butyrolactone; and non-protic polar solvents such asdimethylsulfoxide, N,N-dimethylformamide, and hexamethylphosphorictriamide. These can be used alone or in mixture of two or more thereof.These solvents can be used within a range of 0 to 2,000 parts by massbased on 100 parts by mass of the starting material.

Specific examples of the reaction catalyst include: quaternary ammoniumsalts such as benzyltriethylammonium chloride, benzyltriethylammoniumbromide, benzyltrimethylammonium chloride, tetramethylammonium chloride,tetramethylammonium bromide, tetramethylammonium iodide,tetramethylammonium hydroxide, tetraethylammonium bromide,tetrabutylammonium chloride, tetrabutylammonium bromide,tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, trioctylmethylammonium chloride, tributylbenzylammonium chloride,trimethylbenzylammonium chloride, trimethylbenzylammonium hydroxide,N-laurylpyridinium chloride, N-lauryl-4-picolinium chloride,N-laurylpicolinium chloride, trimethylphenylammonium bromide, andN-benzylpicolinium chloride; quaternary phosphonium salts such astetrabutylphosphonium chloride, tetrabutylphosphonium bromide, andtetraphenylphosphonium chloride; and tertiary amines such astris[2-(2-methoxyethoxy)ethyl]amine, tris(3,6-dioxaheptyl)amine, andtris(3,6-dioxaoctyl)amine. The amount of the catalyst to be used ispreferably in the range of 0.001 to 100 mass %, more preferably 0.005 to50 mass % based on the total amount of the starting material.

The reaction temperature is preferably −50° C. to approximately theboiling point of the solvent, more preferably room temperature to 150°C. The reaction time can be appropriately selected from 0.1 to 100hours.

The reaction method includes: a method where the epoxy compound, thecarboxylic acid compound, and the catalyst are charged at once; a methodof dispersing or dissolving the epoxy compound and the carboxylic acidcompound, then adding the catalyst at once or diluting with a solventand adding dropwise; and a method of dispersing or dissolving thecatalyst, then adding the epoxy compound and the carboxylic acidcompound at once or diluting with a solvent and adding dropwise.

After completion of the reaction in each step, the resultant may be useddirectly as an organic film material, but may also be diluted with anorganic solvent, then subjected to liquid separation and washing toremove unreacted raw materials, the catalyst, and so on present in thesystem, and thus collected.

The organic solvent used in this event is not particularly limited, aslong as the organic solvent is capable of dissolving the compounds andis separated into two layers when mixed with water. The organic solventincludes: hydrocarbons such as hexane, heptane, benzene, toluene, andxylene; esters such as ethyl acetate, n-butyl acetate, and propyleneglycol methyl ether acetate; ketones such as methyl ethyl ketone, methylamyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such asdiethyl ether, diisopropyl ether, methyl-tert-butyl ether, andethylcyclopentylmethyl ether; chlorinated solvents such as methylenechloride, chloroform, dichloroethane, and trichloroethylene; mixturesthereof; and the like. As washing water used in this event, generally,what is called deionized water or ultrapure water may be used. Thewashing may be performed once or more, preferably approximately once tofive times because washing ten times or more does not always produce thefull washing effects thereof.

In the liquid separation and washing, the washing may be performed witha basic aqueous solution to remove the unreacted carboxylic acid oracidic components in the system. The base specifically includeshydroxides of alkaline metals, carbonates of alkaline metals, hydroxidesof alkali earth metals, carbonates of alkali earth metals, ammonia,organic ammonium, and the like.

Further, in the liquid separation and washing, the washing may beperformed with an acidic aqueous solution to remove the metal impuritiesor basic components in the system. The acid specifically includes:inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuricacid, nitric acid, phosphoric acid, and heteropoly acid; organic acidssuch as oxalic acid, trifluoroacetic acid, methanesulfonic acid,benzenesulfonic acid, p-toluenesulfonic acid, andtrifluoromethanesulfonic acid; and the like.

The liquid separation and washing may be performed with any one of thebasic aqueous solution and the acidic aqueous solution, or can beperformed with a combination of the two. The liquid separation andwashing is preferably performed with the basic aqueous solution and theacidic aqueous solution in this order from the viewpoint of removing themetal impurities.

After the liquid separation and washing with the basic aqueous solutionand the acidic aqueous solution, washing with neutral water may besuccessively performed. The washing may be performed once or more,preferably approximately once to five times. As the neutral water,deionized water, ultrapure water, or the like as mentioned above may beused. The washing may be performed once or more, but if the washing isnot performed sufficiently, the basic components and acidic componentscannot be removed in some cases. The washing is preferably performedapproximately once to five times because washing ten times or more doesnot always produce the full washing effects thereof.

Further, the reaction product after the liquid separation can also becollected as a powder by concentrating and drying the solvent orcrystallizing the reaction product under reduced pressure or normalpressure. Alternatively, the reaction product can also be retained inthe state of solution with an appropriate concentration to improve theworkability in preparing the organic film material. The concentration inthis event is preferably 0.1 to 50 mass %, more preferably 0.5 to 30mass %. With such a concentration, the viscosity is hardly increased,making it possible to prevent deterioration of the workability; inaddition, since the amount of the solvent is not excessive, it iseconomical.

The solvent in this event is not particularly limited, as long as thesolvent is capable of dissolving the compound. Specific examples of thesolvent include ketones such as cyclohexanone and methyl-2-amyl ketone;alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol,1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propyleneglycol monomethyl ether, ethylene glycol monomethyl ether, propyleneglycol monoethyl ether, ethylene glycol monoethyl ether, propyleneglycol dimethyl ether, and diethylene glycol dimethyl ether; and esterssuch as propylene glycol monomethyl ether acetate, propylene glycolmonoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate,methyl 3-methoxypropionate, ethyl 3-ethoxy propionate, tert-butylacetate, tert-butyl propionate, and propylene glycol mono-tert-butylether acetate. These can be used alone or in mixture of two or morethereof.

As described, the inventive compound for an organic film material can bemanufactured easily, and can be used suitably for the above-describedinventive material for forming an organic film.

[Material for Forming Organic Film]

The present invention provides a material for forming an organic filmcontaining: (A) the above-described compound; and (B) an organicsolvent. Note that in the inventive material for forming an organicfilm, the above-described compound (A) may be used alone or incombination of two or more thereof.

The organic solvent (component (B)) used in the inventive material forforming an organic film is not particularly limited, but solvents thatdissolve the base polymer, acid generator, crosslinking agent, otheradditives and the like are preferable. Specifically, solvents with aboiling point of lower than 180° C. such as those disclosed inparagraphs (0091) to (0092) of JP 2007-199653 A can be used. Above all,propylene glycol monomethyl ether acetate, propylene glycol monomethylether, 2-heptanone, cyclopentanone, cyclohexanone, and a mixture of twoor more thereof are preferably used. The solvent may also be the same asor different from the solvent used in manufacturing the above-describedcomponent (A).

Such a composition can be applied by spin-coating, and a material forforming an organic film (composition for forming an organic film) havingfavorable dry etching resistance as well as heat resistance and highfilling and planarizing properties can be achieved because the inventivecompound for forming an organic film as described above is incorporated.

Furthermore, the inventive material for forming an organic film may usethe organic solvent with one or more high-boiling-point solvents havinga boiling point of 180° C. or higher added to the above-describedsolvent having a boiling point of lower than 180° C. (a mixture of thesolvent having a boiling point of lower than 180° C. with the solventhaving a boiling point of 180° C. or higher). The high-boiling-pointorganic solvent is not particularly limited to hydrocarbons, alcohols,ketones, esters, ethers, chlorinated solvents, and so forth, as long asthe high-boiling-point organic solvent is capable of dissolving thecompound (A). Specific examples of the high-boiling-point organicsolvent include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol,1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol,2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol,2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropyleneglycol, triethylene glycol, tripropylene glycol, glycerin, ethyleneglycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether,ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether,diethylene glycol monoethyl ether, diethylene glycol monoisopropylether, diethylene glycol mono-n-butyl ether, diethylene glycolmonoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycolmonophenyl ether, diethylene glycol monobenzyl ether, diethylene glycoldiethyl ether, diethylene glycol dibutyl ether, diethylene glycolbutylmethyl ether, triethylene glycol dimethyl ether, triethylene glycolmonomethyl ether, triethylene glycol-n-butyl ether, triethylene glycolbutylmethyl ether, triethylene glycol diacetate, tetraethylene glycoldimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycolmono-n-propyl ether, dipropylene glycol methyl-n-propyl ether,dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethylether, tripropylene glycol monomethyl ether, tripropylene glycolmono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethyleneglycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate,diethylene glycol monomethyl ether acetate, diethylene glycol monoethylether acetate, diethylene glycol monobutyl ether acetate, triacetin,propylene glycol diacetate, dipropylene glycol monomethyl ether acetate,dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate,1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, triethyleneglycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate,propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate,dipropyl succinate, dibutyl succinate, dihexyl succinate, n-nonylacetate, dimethyl adipate, diethyl adipate, dibutyl adipate, and thelike. These may be used alone or in mixture thereof.

The boiling point of the high-boiling-point solvent may be appropriatelyselected according to the temperature at which the material for formingan organic film is heated. The boiling point of the high-boiling-pointsolvent to be added is preferably 180° C. to 300° C., more preferably200° C. to 300° C. Such a boiling point prevents the evaporation rate atbaking (heating) from becoming excessive, which would otherwise occur ifthe boiling point is too low. Thus, the boiling point of 180° C. orhigher can provide sufficient thermal flowability. Meanwhile, with sucha boiling point, the boiling point is not too high, so that thehigh-boiling-point solvent evaporates after baking and does not remainin the film; thus, the boiling point of 300° C. or lower does notadversely affect the film physical properties such as etchingresistance.

When the high-boiling-point solvent is used, the formulation amount ofthe high-boiling-point solvent is preferably 1 to 30 parts by mass basedon 100 parts by mass of the solvent having a boiling point of lower than180° C. The formulation amount in this range prevents a failure inproviding sufficient thermal flowability during baking, which wouldotherwise occur if the formulation amount is too small. In addition,deterioration of the film physical properties such as etching resistanceis prevented, which would otherwise occur if the formulation amount isso large that the solvent remains in the film.

With such an organic film composition, the above-described compound forforming an organic film is provided with thermal flowability by addingthe high-boiling-point solvent, so that the composition for forming anorganic film also has high filling and planarizing properties.

Besides the components (A) and (B), the inventive material for formingan organic film may contain other components as necessary.

[Blend Compound, etc.]

The inventive material for forming an organic film may be furtherblended with a different compound or polymer. The blend compound orblend polymer mixed with the inventive material for forming an organicfilm serves to improve the film-formability with spin-coating and thefilling property for a stepped substrate. Examples of such a materialinclude novolak resins of phenol, o-cresol, m-cresol, p-cresol,2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol,3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol,2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol,3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol,4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol,4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol,4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol,2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol,4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol,2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, pyrogallol,thymol, isothymol, 4,4′-(9H-fluorene-9-ylidene)bisphenol,2,2′dimethyl-4,4′-(9H-fluorene-9-ylidene)bisphenol,2,2′diallyl-4,4′-(9H-fluorene-9-ylidene)bisphenol,2,2′difluoro-4,4′-(9H-fluorene-9-ylidene)bisphenol,2,2′diphenyl-4,4′-(9H-fluorene-9-ylidene)bisphenol,2,2′dimethoxy-4,4′-(9H-fluorene-9-ylidene)bisphenol,2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol,3,3,3′,3′-tetramethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol,3,3,3′,3′,4,4′-hexamethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol,2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-5,5′-diol,5,5′-dimethyl-3,3,3′,3′-tetramethyl-2,3,2′,3′-tetrahydro-(1,1′)-spirobiindene-6,6′-diol,1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, and7-methoxy-2-naphthol, dihydroxynaphthalenes such as1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and2,6-dihydroxynaphthalene, methyl 3-hydroxynaphthalene-2-carboxylate,indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene,biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene,4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, α-pinene,β-pinene, limonene, etc.; and polyhydroxystyrene, polystyrene,polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole,polyindene, polyacenaphthylene, polynorbornene, poly cyclodecene,polytetracyclododecene, polynortricyclene, poly(meth)acrylate, andcopolymers thereof. It is also possible to blend a naphtholdicyclopentadiene copolymer disclosed in JP 2004-205685 A, a fluorenebisphenol novolak resin disclosed in JP 2005-128509 A, an acenaphthylenecopolymer disclosed in JP 2005-250434 A, fullerene having a phenol groupdisclosed in JP 2006-227391 A, a bisphenol compound and a novolak resinthereof disclosed in JP 2006-293298 A, a novolak resin of an adamantanephenol compound disclosed in JP 2006-285095 A, a bisnaphthol compoundand a novolak resin thereof disclosed in JP 2010-122656 A, a fullereneresin compound disclosed in JP 2008-158002 A, or the like. The blendcompound or the blend polymer is blended in an amount of preferably 0 to1,000 parts by mass, more preferably 0 to 500 parts by mass, based on100 parts by mass of the inventive organic film material.

[Acid Generator]

In the inventive organic film material, an acid generator can be addedso as to further promote the curing reaction. The acid generatorincludes a material that generates an acid by thermal decomposition, anda material that generates an acid by light irradiation. Any acidgenerator can be added. Specifically, materials disclosed in paragraphs(0061) to (0085) of JP 2007-199653 A can be added, but the presentinvention is not limited thereto.

The acid generators can be used alone or in combination of two or morethereof. When the acid generator is added, the added amount ispreferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, based on100 parts of the compound.

[Surfactant]

To the inventive organic film material, a surfactant can be added so asto enhance the coating property in spin-coating. As examples of thesurfactant, those disclosed in (0142) to (0147) of JP 2009-269953 A canbe used.

[Crosslinking Agent]

Moreover, to the composition for forming an organic film of the presentinvention, a crosslinking agent can also be added so as to increase thecurability and to further suppress intermixing with a resist upper layerfilm. The crosslinking agent is not particularly limited, and knownvarious types of crosslinking agents can be widely used. Examplesthereof include melamine-based crosslinking agents, methylol ormethoxymethyl-type crosslinking agents of polynuclear phenols,glycoluril-based crosslinking agents, benzoguanamine-based crosslinkingagents, urea-based crosslinking agents, β-hydroxyalkylamide-basedcrosslinking agents, isocyanurate-based crosslinking agents,aziridine-based crosslinking agents, oxazoline-based crosslinkingagents, and epoxy-based crosslinking agents.

Specific examples of the melamine-based crosslinking agents includehexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy-and/or hydroxy-substituted derivatives thereof, and partialself-condensates thereof.

Examples of the methoxymethyl type crosslinking agents of polynuclearphenols include tetramethylated and tetramethoxymethylated bisphenolssuch as bisphenol A and bisphenol F, hexamethoxymethylated trisphenolssuch as triphenolmethane, triphenolethane,1,1,1-tris(4-hydroxyphenyl)ethane,tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, and partialcondensates thereof.

Specific examples of the glycoluril-based crosslinking agents includetetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril,alkoxy- and/or hydroxy-substituted derivatives thereof, and partialself-condensates thereof.

Specific examples of the benzoguanamine-based crosslinking agentsinclude tetramethoxymethylated benzoguanamine, tetrabutoxymethylatedbenzoguanamine, alkoxy- and/or hydroxy-substituted derivatives thereof,and partial self-condensates thereof.

Specific examples of the urea-based crosslinking agents includedimethoxymethylated dimethoxyethyleneurea, alkoxy- and/orhydroxy-substituted derivatives thereof, and partial self-condensatesthereof.

A specific example of the O-hydroxyalkylamide-based crosslinking agentsincludes N,N,N′,N′-tetra(2-hydroxyethyl)adipic acid amide.

Specific examples of the isocyanurate-based crosslinking agents includetriglycidyl isocyanurate and triallyl isocyanurate.

Specific examples of the aziridine-based crosslinking agents include4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

Specific examples of the oxazoline-based crosslinking agents include2,2′-isopropylidene bis(4-benzyl-2-oxazoline), 2,2′-isopropylidenebis(4-phenyl-2-oxazoline), 2,2′-methylenebis4,5-diphenyl-2-oxazoline,2,2′-methylenebis-4-phenyl-2-oxazoline,2,2′-methylenebis-4-tert-butyl-2-oxazoline, 2,2′-bis(2-oxazoline),1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and a2-isopropenyloxazoline copolymer.

Specific examples of the epoxy-based crosslinking agents includediglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanedioldiglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether,poly(glycidyl methacrylate), trimethylolethane triglycidyl ether,trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidylether.

[Plasticizer]

Further, to the inventive organic film material, a plasticizer can beadded so as to further enhance the high filling and planarizingproperties. The plasticizer is not particularly limited, and knownvarious types of plasticizers can be widely used. Examples thereofinclude low-molecular-weight compounds such as phthalic acid esters,adipic acid esters, phosphoric acid esters, trimellitic acid esters, andcitric acid esters; and polymers such as polyethers, polyesters, andpolyacetal-based polymers disclosed in JP 2013-253227 A.

[Other Additives]

Particularly, like the plasticizer, as an additive for providing thecomposition for forming an organic film of the present invention withfilling and planarizing properties, it is preferable to use, forexample, liquid additives having polyethylene glycol and polypropyleneglycol structures, or thermo-decomposable polymers having a weight lossratio between 30° C. and 250° C. of 40 mass % or more and aweight-average molecular weight of 300 to 200,000. Thethermo-decomposable polymers preferably contain a repeating unit havingan acetal structure shown by the following general formula (DP1) or(DP1a).

(In the formula, R₄ represents a hydrogen atom or a saturated orunsaturated monovalent organic group having 1 to 30 carbon atoms whichmay be substituted. Y₁ represents a saturated or unsaturated divalentorganic group having 2 to 30 carbon atoms.)

(In the formula, R_(4a) represents an alkyl group having 1 to 4 carbonatoms. Y^(a) represents a saturated or unsaturated divalent hydrocarbongroup having 4 to 10 carbon atoms which may have an ether bond. “n”represents an average repeating unit number of 3 to 500.)

Note that the inventive material for forming an organic film can be usedalone or in combination of two or more thereof. In particular, thematerial for forming an organic film can be used for a resist underlayerfilm material or a planarizing material for manufacturing asemiconductor device.

In addition, the inventive material for forming an organic film isextremely useful as a resist underlayer film material in a multilayerresist process such as a 2-layer resist process, a 3-layer resistprocess using a middle layer film containing a silicon atom, or a4-layer resist process using an inorganic hard mask middle layer filmcontaining a silicon atom and an organic antireflective coating.

[Substrate for Manufacturing Semiconductor Device]

Additionally, the present invention can provide a substrate formanufacturing a semiconductor device, including an organic film on thesubstrate, the organic film being formed by curing the above-describedmaterial for forming an organic film.

A resist underlayer film obtained by curing the inventive material forforming an organic film has high filling and planarizing properties andadhesion to a substrate, and accordingly, the resist underlayer filmdoes not have fine pores due to insufficient filling, asperity in theresist underlayer film surface due to insufficient planarizing property,or film delamination when forming the inorganic hard mask middle layerfilm directly on the resist underlayer film. A substrate formanufacturing a semiconductor device planarized by such a resistunderlayer film has an increased process margin at patterning, making itpossible to manufacture semiconductor devices with high yields.

[Method for Forming Organic Film]

The present invention provides a method for forming an organic filmwhich serves as a resist underlayer film in a multilayer resist filmused in lithography or a planarizing film for manufacturing asemiconductor by using the above-described organic film material.

In the inventive method for forming an organic film, a substrate to beprocessed is coated with the organic film material by a spin-coatingmethod etc. By employing a method like spin-coating method, favorablefilling property can be obtained. After the spin-coating, baking(heating) is performed to evaporate the solvent and to promote thecrosslinking reaction, thereby preventing the mixing with a resist upperlayer film or a resist middle layer film. The baking is preferablyperformed at 100° C. or higher to 600° C. or lower for 10 to 600seconds, more preferably at 200° C. or higher to 500° C. or lower for 10to 300 seconds. In considering the influences of device damage and waferdeformation, the upper limit of the heating temperature in lithographicwafer process is preferably 600° C. or lower, more preferably 500° C. orlower.

Moreover, in the inventive method for forming an organic film, after asubstrate to be processed is coated with the inventive organic filmmaterial by the spin-coating method or the like as described above, anorganic film can be formed by curing the organic film material by baking(heating) in an atmosphere with an oxygen concentration of 0.1% or moreto 21% or less.

The organic film material of the present invention is baked in such anoxygen atmosphere, thereby enabling to obtain a fully cured film.

The atmosphere during the heating may be in air, or an inert gas such asN₂, Ar, and He may be introduced. In addition, the heating temperature,etc. can be the same as described above.

As the substrate to be processed, a substrate to be processed having astructure or a step with a height of 30 nm or more can be used.

Because of the high filling and planarizing properties, the inventivemethod for forming an organic film as described above can provide a flatcured film regardless of unevenness of a substrate to be processed.Accordingly, the inventive method is particularly useful in forming aflat cured film on a substrate to be processed having a structure or astep with a height of 30 nm or more.

[Patterning Process]

The present invention provides a patterning process according to a3-layer resist process using the material for forming an organic film asdescribed above. The patterning process is a method for forming apattern in a body to be processed, and includes at least the followingsteps:

forming a resist underlayer film by using the inventive material forforming an organic film on the body to be processed;

forming a resist middle layer film (silicon-atom-containing resistmiddle layer film) by using a resist middle layer film materialcontaining a silicon atom on the resist underlayer film;

forming a resist upper layer film by using a resist upper layer filmmaterial including a photoresist composition on the resist middle layerfilm so that a multilayer resist film is constructed;

forming a resist pattern (circuit pattern) in the resist upper layerfilm by exposing a pattern circuit region of the resist upper layerfilm, then developing with a developer;

transferring the pattern to the resist middle layer film by etching theresist middle layer film while using the resist upper layer film havingthe formed resist pattern as an etching mask;

transferring the pattern to the resist underlayer film by etching theresist underlayer film while using the obtained resist middle layer filmpattern as an etching mask; and

further forming the pattern on the substrate to be processed by etchingthe substrate to be processed while using the resist underlayer filmpattern as an etching mask.

The silicon-atom-containing resist middle layer film in the 3-layerresist process exhibits resistance to etching by an oxygen gas or ahydrogen gas. Thus, when the resist underlayer film is etched whileusing the resist middle layer film as a mask in the 3-layer resistprocess, the etching is preferably performed using an etching gas mainlycontaining an oxygen gas or a hydrogen gas.

As the silicon-atom-containing resist middle layer film in the 3-layerresist process, a polysilsesquioxane-based middle layer film is alsofavorably used. The resist middle layer film having an antireflectiveeffect can suppress the reflection. Particularly, for 193-nm lightexposure, a material containing many aromatic groups and having highsubstrate etching resistance is used as a resist underlayer film, sothat the k-value and thus the substrate reflection are increased.However, the reflection can be suppressed by the resist middle layerfilm, and so the substrate reflection can be reduced to 0.5% or less. Asthe resist middle layer film having the antireflective effect, apolysilsesquioxane is preferably used, the polysilsesquioxane havinganthracene for 248-nm and 157-nm light exposure, or a phenyl group or alight-absorbing group having a silicon-silicon bond for 193-nm lightexposure in a pendant structure, and being crosslinked by an acid orheat.

In this case, forming a silicon-containing resist middle layer film by aspin-coating method is simpler and more advantageous regarding cost thana CVD method.

In addition, a 4-layer resist process using an organic antireflectivecoating is also favorable, and in this case, a pattern can be formed ona body to be processed by performing at least the following steps:

forming a resist underlayer film by using the inventive material forforming an organic film on the body to be processed;

forming a resist middle layer film (silicon-atom-containing resistmiddle layer film) by using a resist middle layer film materialcontaining a silicon atom on the resist underlayer film;

forming a BARC (organic antireflective coating) on the resist middlelayer film;

forming a resist upper layer film by using a resist upper layer filmmaterial being a photoresist composition on the BARC so that amultilayer resist film is constructed;

forming a resist pattern (circuit pattern) in the resist upper layerfilm by exposing a pattern circuit region of the resist upper layerfilm, then developing with a developer;

transferring the pattern to the resist middle layer film by etching theBARC and the resist middle layer film while using the resist pattern asan etching mask;

transferring the pattern to the resist underlayer film by etching theresist underlayer film while using the resist middle layer film patternas an etching mask; and

further forming the pattern on the body to be processed by etching thebody to be processed while using the resist underlayer film pattern asan etching mask.

In addition, an inorganic hard mask middle layer film can be formed as amiddle layer film, and in this case, a pattern can be formed on a bodyto be processed by performing at least the following steps:

forming a resist underlayer film by using the inventive material forforming an organic film on a body to be processed;

forming an inorganic hard mask middle layer film selected from a siliconoxide film, a silicon nitride film, and a silicon oxynitride film on theresist underlayer film;

forming a resist upper layer film by using a resist upper layer filmmaterial including a photoresist composition on the inorganic hard maskmiddle layer film;

forming a resist pattern (circuit pattern) in the resist upper layerfilm by exposing a pattern circuit region of the resist upper layerfilm, then developing with a developer;

transferring the pattern to the inorganic hard mask middle layer film byetching the inorganic hard mask middle layer film while using the resistpattern as an etching mask;

transferring the pattern to the resist underlayer film by etching theresist underlayer film while using the inorganic hard mask middle layerfilm pattern as an etching mask; and

further forming the pattern on the body to be processed by etching thebody to be processed while using the resist underlayer film pattern asan etching mask.

In the case where an inorganic hard mask middle layer film is formed onthe resist underlayer film as described above, a silicon oxide film, asilicon nitride film, and a silicon oxynitride film (SiON film) can beformed by a CVD method, an ALD method, or the like. The method forforming the silicon nitride film is disclosed in, for example, JP2002-334869 A and WO 2004/066377 A1. The film thickness of the inorganichard mask middle layer film is preferably 5 to 200 nm, more preferably10 to 100 nm. As the inorganic hard mask middle layer film, a SiON filmis most preferably used, being effective as an antireflective coating.When the SiON film is formed, the substrate temperature reaches 300 to500° C. Hence, the underlayer film needs to withstand the temperature of300 to 500° C. Since the materials for forming an organic film used inthe present invention have high heat resistance and can withstand hightemperatures of 300° C. to 500° C., the combination of the inorganichard mask middle layer film formed by a CVD method or an ALD method withthe resist underlayer film formed by a spin-coating method is possible.

Formation of an inorganic hard mask middle layer film is also suitablefor a 4-layer resist process using an organic antireflective coating,and in this case, a pattern can be formed on a body to be processed byperforming at least the following steps:

forming a resist underlayer film by using the inventive material forforming an organic film on the body to be processed;

forming an inorganic hard mask middle layer film selected from a siliconoxide film, a silicon nitride film, and a silicon oxynitride film on theresist underlayer film;

forming a BARC (organic antireflective coating) on the inorganic hardmask middle layer film;

forming a resist upper layer film by using a resist upper layer filmmaterial being a photoresist composition on the BARC so that amultilayer resist film is constructed;

forming a resist pattern (circuit pattern) in the resist upper layerfilm by exposing a pattern circuit region of the resist upper layerfilm, then developing with a developer;

transferring the pattern to the inorganic hard mask middle layer film byetching the BARC and the inorganic hard mask middle layer film whileusing the resist pattern as an etching mask;

transferring the pattern to the resist underlayer film by etching theresist underlayer film while using the inorganic hard mask middle layerfilm pattern as an etching mask; and

further forming the pattern on the body to be processed by etching thebody to be processed while using the resist underlayer film pattern asan etching mask.

The photoresist film may be formed directly on the inorganic hard maskmiddle layer film as a resist upper layer film as described above, oralternatively, it is also possible to form a BARC (organicantireflective coating) on the inorganic hard mask middle layer film byspin-coating, and then form a photoresist film thereon. In particular,when a SiON film is used as the inorganic hard mask middle layer film,two antireflective coatings including the SiON film and the BARC make itpossible to suppress the reflection even in liquid immersion exposure ata high NA exceeding 1.0. Another advantage of the BARC formation ishaving an effect of reducing trailing of the photoresist patternimmediately above the SiON film.

The resist upper layer film in the 3-layer or 4-layer resist process maybe a positive type or a negative type, and any generally-usedphotoresist composition can be employed. After spin-coating of thephotoresist composition, pre-baking is preferably performed at 60 to180° C. for 10 to 300 seconds. Then, light exposure, PEB (post-exposurebake), and development are performed according to conventional methodsto obtain the resist pattern. Note that the thickness of the resistupper layer film is not particularly limited, but is preferably 30 to500 nm, and 50 to 400 nm is particularly preferable.

A circuit pattern (resist upper layer film pattern) is formed in theresist upper layer film, and in the circuit pattern formation, thecircuit pattern is preferably formed by a photolithography with awavelength of 10 nm or more to 300 nm or less, a direct drawing byelectron beam, a nanoimprinting, or a combination thereof.

Note that examples of exposure light include a high-energy beam with awavelength of 300 nm or less, specifically, deep ultraviolet ray, KrFexcimer laser beam (248 nm), ArF excimer laser beam (193 nm), F₂ laserbeam (157 nm), Kr laser beam (146 nm), Ar laser beam (126 nm), softX-ray of 3 to 20 nm (EUV), electron beam (EB), ion beam, X-ray, and thelike.

Additionally, in forming the circuit pattern, the circuit pattern ispreferably developed by alkaline development or development with anorganic solvent.

Next, etching is performed while using the obtained resist upper layerfilm pattern as an etching mask. In the 3-layer resist process, theresist middle layer film and the inorganic hard mask middle layer filmare etched using a fluorocarbon-based gas and using the resist upperlayer film pattern as the etching mask. Thereby, a resist middle layerfilm pattern and an inorganic hard mask middle layer film pattern areformed.

Next, the resist underlayer film is etched while using the obtainedresist middle layer film pattern and inorganic hard mask middle layerfilm pattern as etching masks.

Subsequently, the substrate to be processed can be etched according to aconventional method. For example, the substrate to be processed made ofSiO₂, SiN, or silica-based low-dielectric insulating film is etchedmainly with a fluorocarbon-based gas; and p-Si, Al, or W is etchedmainly with a chlorine- or bromine-based gas. When the substrate isprocessed by etching with a fluorocarbon-based gas, thesilicon-atom-containing middle layer film pattern in the 3-layer resistprocess is removed when the substrate is processed. When the substrateis etched with a chlorine- or bromine-based gas, the silicon-containingmiddle layer film pattern needs to be removed by additional dry etchingwith a fluorocarbon-based gas after the substrate processing.

Furthermore, the body to be processed can be a semiconductor devicesubstrate or the semiconductor device substrate coated with any of ametal film, a metal carbide film, a metal oxide film, a metal nitridefilm, a metal oxycarbide film, or a metal oxynitride film.

Furthermore, the body to be processed can be metallic silicon, titanium,tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold,aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium,cobalt, manganese, molybdenum, or an alloy thereof.

A resist underlayer film obtained from the inventive material forforming an organic film has a characteristic of being excellent inetching resistance when etching these bodies to be processed.

Note that the body to be processed is not particularly limited, andexamples of the semiconductor device substrate include: substrates madeof Si, α-Si, p-Si, SiO₂, SiN, SiON, W, TiN, Al, or the like; the body tobe processed coated with a layer to be processed; etc. Examples of thelayer to be processed include: various Low-k films made of Si, SiO₂,SiON, SiN, p-Si, α-Si, W, W—Si, Al, Cu, Al—Si, or the like; and stopperfilms thereof. Generally, the layer can be formed to have a thickness of50 to 10,000 nm, in particular, 100 to 5,000 nm. Note that when thelayer to be processed is formed, the body to be processed and the layerto be processed are formed from different materials.

Hereinbelow, an example of the 3-layer resist process will bespecifically described with reference to FIG. 1.

As shown in FIG. 1 (A), in the 3-layer resist process, a resistunderlayer film 3 is formed by using the inventive material for formingan organic film on a layer 2 to be processed that has been stacked on asubstrate 1 to be processed. Then, a silicon-atom-containing resistmiddle layer film 4 is formed, and a resist upper layer film 5 is formedthereon.

Next, as shown in FIG. 1 (B), a predetermined portion (exposed portion6) of the resist upper layer film 5 is exposed to light, followed by PEBand development to form a resist upper layer film pattern 5 a (FIG. 1(C)). While using the obtained resist upper layer film pattern 5 a as anetching mask, the silicon-atom-containing resist middle layer film 4 isetched with a CF-based gas. Thereby, a silicon-atom-containing resistmiddle layer film pattern 4 a is formed (FIG. 1 (D)). After the resistupper layer film pattern 5 a is removed, the resist underlayer film 3 isetched with oxygen plasma while using the obtainedsilicon-atom-containing resist middle layer film pattern 4 a as anetching mask. Thereby, a resist underlayer film pattern 3 a is formed(FIG. 1 (E)). Further, after the silicon-atom-containing resist middlelayer film pattern 4 a is removed, the layer 2 to be processed is etchedwhile using the resist underlayer film pattern 3 a as an etching mask.Thus, a pattern 2 a is formed (FIG. 1 (F)).

When an inorganic hard mask middle layer film is used, thesilicon-atom-containing resist middle layer film 4 is the inorganic hardmask middle layer film, and when a BARC is formed, the BARC is disposedbetween the silicon-atom-containing resist middle layer film 4 and theresist upper layer film 5. The etching of the BARC may be performedcontinuously before the etching of the silicon-atom-containing resistmiddle layer film 4. Alternatively, after the BARC is etched alone, theetching apparatus is changed, for example, and then the etching of thesilicon-atom-containing resist middle layer film 4 may be performed.

As described above, the inventive patterning processes make it possibleto precisely form a fine pattern in a substrate to be processed in themultilayer resist processes.

EXAMPLE

Hereinafter, the present invention will be more specifically describedwith reference to Synthesis Examples, Comparative Synthesis Examples,Examples, and Comparative Examples. However, the present invention isnot limited thereto. Note that, specifically, the molecular weight wasmeasured by the following method.

[Molecular Weight Measurement]

Weight-average molecular weight (Mw) and number-average molecular weight(Mn) were measured by GPC (gel permeation chromatography) usingtetrahydrofuran as an eluent in terms of polystyrene, and dispersity(Mw/Mn) was calculated therefrom.

Synthesis Examples: Synthesis of Compounds Used in Organic Film Material

Polymers (A1) to (A28) for organic film materials were synthesized usingepoxy compounds (Compounds B: (B1) to (B14)) and carboxylic acidcompounds (Compounds C: (C1) to (C8)) shown below.

Compounds B:

Except for the following, purchased reagents were used.

(B1) EXA-850CRP (manufactured by DIC Corporation) epoxy equivalent: 172(B2) HP-4700 (manufactured by DIC Corporation) epoxy equivalent: 165(B3) HP-4770 (manufactured by DIC Corporation) epoxy equivalent: 205(B5) 1032H60 (manufactured by Mitsubishi Chemical Corporation) epoxyequivalent: 167(B10) DAG-G (manufactured by Shikoku Chemical Corporation) epoxyequivalent: 168(B11) TG-G (manufactured by Shikoku Chemical Corporation) epoxyequivalent: 92(B13) Epolite MF (manufactured by Kyoei Kagaku Kogyo Co., Ltd) epoxyequivalent: 140(B14) PETG (manufactured by Showa Denko K. K.) epoxy equivalent: 90

Compounds C:

Synthesis of Carboxylic Acid Compound (C1)

To a mixture of 10.0 g of succinic anhydride and 50 g ofN,N-dimethylformamide, 6.16 g of propargyl alcohol was slowly addeddropwise. The solution was stirred under a nitrogen atmosphere at roomtemperature for 30 minutes, then the inner temperature was raised to 40°C., and the solution was stirred for 24 hours. After cooling by allowingto stand, 50 mL of a 20% aqueous hydrochloric acid was added, and thereaction was stopped. 100 g of ethyl acetate was added, the resultantwas washed three times with 100 g pure water, and the organic layer wasevaporated under reduced pressure to dryness. To the residue, 100 g oftoluene was added to form a homogeneous solution, then a crystal wasprecipitated with 200 g of hexane. The precipitated crystal wasseparated by filtration, washed twice with 100 g of hexane, andcollected. The collected crystal was vacuum dried at 70° C. Thus,carboxylic acid compound (C1) was obtained at a yield of 32%.

Synthesis of Carboxylic Acid Compound (C2)

Carboxylic acid compound (C2) was obtained under the same reactionconditions as carboxylic acid compound (C1) except for the usedcarboxylic acid anhydride.

Synthesis of Carboxylic Acid Compound (C3)

To a mixture of 10.0 g of succinic anhydride and 40 g ofN,N-dimethylformamide, a solution of 12.06 g of 3-ethynylanilinedissolved in 10 g of N,N-dimethylformamide was slowly added dropwise.The resultant was stirred under a nitrogen atmosphere at roomtemperature for 24 hours. After cooling by allowing to stand, 100 g ofethyl acetate was added, the resultant was washed three times with 100 gof pure water, and the organic layer was evaporated under reducedpressure to dryness. To the residue, 100 g of toluene was added to forma homogeneous solution, then a crystal was precipitated in an ice bath.The precipitated crystal was separated by filtration, washed twice with100 g of toluene, and collected. The collected crystal was vacuum driedat 70° C. Thus, carboxylic acid compound (C3) was obtained at a yield of47%.

Synthesis of Carboxylic Acid Compounds (C4) to (C8)

Carboxylic acid compounds (C4) to (C8) were obtained under the samereaction conditions as carboxylic acid compound (C3) except for the usedcarboxylic acid anhydrides and amine compounds.

[Synthesis Example 1] Synthesis of Compound (A1)

A homogeneous solution of 10.0 g of an epoxy compound (B1), 9.08 g of acarboxylic acid compound (C1), and 100 g of 2-methoxy-1-propanol wasformed under a nitrogen atmosphere at an inner temperature of 100° C.Then, 0.69 g of benzyltriethylammonium chloride was added, and wasstirred at an inner temperature of 120° C. for 12 hours. After coolingto room temperature, 200 ml of methyl isobutyl ketone was added, and theresultant was washed twice with 100 g of a 2% NaHCO₃ aqueous solutionand 100 g of a 3% nitric acid aqueous solution, and five times with 100g of ultrapure water. The organic layer was evaporated under reducedpressure to dryness to obtain compound (Al). When the weight-averagemolecular weight (Mw) and dispersity (Mw/Mn) were measured by GPC, theresults were: Mw=1030; Mw/Mn=1.04.

[Synthesis Examples 2 to 28] Synthesis of Compounds (A2) to (A28)

Except that the epoxy compounds and the carboxylic acid compounds shownin Table 1 to Table 4 were used, the compounds (A2) to (A28) shown inTable 1 to Table 4 were obtained as products under the same reactionconditions as Synthesis Example 1. The Mw (weight-average molecularweight) and the dispersity (Mw/Mn) of these compounds were determinedand shown in Table 5.

TABLE 1 Carboxylic Synthesis Epoxy acid Example compound compoundProduct A1 B1 10.0 g C1 9.1 g

  (A1) A2 B1 10.0 g C5 13.4 g

  (A2) A3 B1 10.0 g C6 15.4 g

  (A3) A4 B1 10.0 g C7 15.4 g

  (A4) A5 B2 10.0 g C1 9.5 g

  (A5) A6 B2 10.0 g C3 13.2 g

  (A6) A7 B2 10.0 g C5 14.0 g

  (A7) A8 B2 10.0 g C6 16.1 g

  (A8)

TABLE 2 Carboxylic Synthesis Epoxy acid Example compound compoundProduct A9  B2 10.0 g C7 16.1 g

  (A9) A10 B3 10.0 g C2 10.0 g

  (A10) A11 B3 10.0 g C6 12.9 g

  (A11) A12 B4 10.0 g C4 9.9 g

  (A12) A13 B4 10.0 g C5 9.9 g

  (A13) A14 B5 10.0 g C7 15.9 g

  (A14) A15 B6 5.0 g C7 12.5 g

  (A15) A16 B7 10.0 g C67 17.9 g

  (A16)

TABLE 3 Carboxylic Synthesis Epoxy acid Example compound compoundProduct A17 B8 10.0 g C2 14.5 g

  (A17) A18 B8 10.0 g C5 16.4 g

  (A18) A19 B8 10.0 g C6 18.9 g

  (A19) A20 B8 10.0 g C8 11.0 g

  (A20) A21 B9 10.0 g C2 20.6 g

  (A21) A22 B9 10.0 g C5 23.3 g

  (A22) A23 B9 10.0 g C6 26.8 g

  (A23)

TABLE 4 Carboxylic Synthesis Epoxy acid Example compound compoundProduct A24 B10 10.0 g C7 15.8 g

  (A24) A25 B11 5.0 g C7 14.4 g

  (A25) A26 B12 5.0 g C7 13.1 g

  (A26) A27 B13 10.0 g C7 18.9 g

  (A27) A28 B14 5.0 g C7 14.7 g

  (A28)

TABLE 5 Synthesis Example Compound Mw (GPC) Mw/Mn 1  (A1) 1030 1.04 2 (A2) 1010 1.05 3  (A3) 1050 1.07 4  (A4) 1100 1.08 5  (A5) 1830 1.33 6 (A6) 1850 1.33 7  (A7) 1900 1.35 8  (A8) 2220 1.40 9  (A9) 2170 1.38 10(A10) 1250 1.25 11 (A11) 1310 1.27 12 (A12) 1270 1.04 13 (A13) 1240 1.0414 (A14) 1530 1.34 15 (A15) 830 1.03 16 (A16) 1180 1.07 17 (A17) 10201.03 18 (A18) 1080 1.02 19 (A19) 1100 1.04 20 (A20) 980 1.02 21 (A21)1170 1.05 22 (A22) 1240 1.08 23 (A23) 1180 1.05 24 (A24) 1070 1.03 25(A25) 1350 1.10 26 (A26) 890 1.03 27 (A27) 1200 1.05 28 (A28) 1530 1.09

[Comparative Synthesis Example 1] Synthesis of Compound (R1)

A homogeneous solution of 20.0 g of an epoxy compound (B2), 17.7 g of4-ethynylbenzoic acid, and 200 g of 2-methoxy-1-propanol was formedunder a nitrogen atmosphere at an inner temperature of 100° C. Then,1.00 g of benzyltriethylammonium chloride was added, and was stirred atan inner temperature of 120° C. for 12 hours. After cooling to roomtemperature, 300 ml of methyl isobutyl ketone was added, and theresultant was washed twice with 100 g of a 2% NaHCO₃ aqueous solutionand 100 g of a 3% nitric acid aqueous solution, and five times with 100g ultrapure water. The organic layer was evaporated under reducedpressure to dryness to obtain compound (R1). When the weight-averagemolecular weight (Mw) and dispersity (Mw/Mn) were measured by GPC, theresults were: Mw=1740; Mw/Mn=1.33.

[Comparative Synthesis Example 2] Synthesis of Compound (R2)

A homogeneous solution of 20.0 g of an epoxy compound (B2), 23.3 g of a4-butoxybenzoic acid, and 200 g of 2-methoxy-1-propanol was formed undera nitrogen atmosphere at an inner temperature of 100° C. Then, 1.00 g ofbenzyltriethylammonium chloride was added, and was stirred at an innertemperature of 120° C. for 12 hours. After cooling to room temperature,300 ml of methyl isobutyl ketone was added, and the resultant was washedtwice with 100 g of a 2% NaHCO₃ aqueous solution and 100 g of a 3%nitric acid aqueous solution, and five times with 100 g of ultrapurewater. The organic layer was evaporated under reduced pressure todryness to obtain compound (R2). When the weight-average molecularweight (Mw) and dispersity (Mw/Mn) were measured by GPC, the resultswere: Mw=1930; Mw/Mn=1.32.

[Comparative Synthesis Example 3] Synthesis of Compound (R3)

A homogeneous solution of 20.0 g of an epoxy compound (B2), 16.7 g of a4-hydroxybenzoic acid, and 200 g 2-methoxy-1-propanol was formed under anitrogen atmosphere at an inner temperature of 100° C. Then, 1.00 g ofbenzyltriethylammonium chloride was added, and was stirred at an innertemperature of 120° C. for 12 hours. After cooling to room temperature,300 ml of methyl isobutyl ketone was added, and the resultant was washedtwice with 100 g of a 2% NaHCO₃ aqueous solution and 100 g of a 3%nitric acid aqueous solution, and five times with 100 g of ultrapurewater. The organic layer was evaporated under reduced pressure todryness to obtain compound (R3). When the weight-average molecularweight (Mw) and dispersity (Mw/Mn) were measured by GPC, the resultswere: Mw=1610; Mw/Mn=1.35.

[Comparative Synthesis Example 4] Synthesis of Compound (R4)

17.4 g of 9,9-bis-(4-aminophenyl)fluorene, 16.5 g of 4-ethylbenzoylchloride, 5.1 g of triethyl amine, and 150 g of N,N-dimethylacetamidewere stirred under a nitrogen atmosphere at a liquid temperature of 0°C. for 1 hour. Then the temperature was raised to room temperature, andthe resultant was stirred for 3 hours. After completion of the reaction,500 g of methyl isobutyl ketone was added, the organic layer was washedfive times with 200 g of pure water. Then, the organic layer wasevaporated under reduced pressure to dryness. To the residue, 300 mL ofTHF was added, and the polymer was reprecipitated with 1,000 mL ofhexane. The precipitated polymer was separated by filtration, and driedunder reduced pressure. Thus, compound (R4) was obtained. When theweight-average molecular weight (Mw) and dispersity (Mw/Mn) weremeasured by GPC, the results were: Mw=1,150; Mw/Mn=1.03.

[Comparative Synthesis Example 5] Synthesis of Compound (R5)

A homogeneous solution of 10.0 g of an epoxy compound (B9), 9.9 g ofsuccinic anhydride, and 50 g of 2-methoxy-1-propanol was formed under anitrogen atmosphere at an inner temperature of 100° C. Then, 0.50 g ofbenzyltriethylammonium chloride was added, and was stirred at an innertemperature of 120° C. for 12 hours. After cooling to room temperature,200 ml of methyl isobutyl ketone was added, and the resultant was washedtwice with 50 g of a 2% NaHCO₃ aqueous solution and 50 g of a 3% nitricacid aqueous solution, and five times with 50 g of ultrapure water. Theorganic layer was evaporated under reduced pressure to dryness to obtaincompound (R5). When the weight-average molecular weight (Mw) anddispersity (Mw/Mn) were measured by GPC, the results were: Mw=1320;Mw/Mn=1.17.

None of the compounds (R1) to (R5) contains a group shown by the generalformulae (3) of the present invention.

Preparation of (UDL-1 to -30, Comparative UDL-1 to -5)

The following were used: the compounds (A1) to (A28) and comparativecompounds (R1) to (R5); (S1) 1,6-diacetoxyhexane having a boiling pointof 260° C. and (S2) tripropylene glycol monomethyl ether having aboiling point of 242° C. as high-boiling-point solvents; XL1 as acrosslinking agent; and AG1 as a thermal acid generator. Using propyleneglycol monomethyl ether acetate (PGMEA) containing 0.1 mass % of PF636(manufactured by OMNOVA), being a surfactant, the compounds weredissolved in proportions shown in Table 6. The solution was thenfiltered through a 0.1-μm filter made of a fluorinated resin to preparecompositions (UDL-1 to -30, comparative UDL-1 to -5) for forming anorganic film.

Incidentally, PGME and CyHO are solvents.

The structural formulae of the crosslinking agent (XL1) and the acidgenerator (AG1) used in Comparative Examples UDL are shown below.

TABLE 6 High- boiling- Crosslinking Acid point Organic Compound agentgenerator solvent PGMEA PGME CyHO Film (parts (parts (parts (parts(parts (parts (parts Material by mass) by mass) by mass) by mass) bymass) by mass) by mass) UDL-1  A1 (10) — — — 90 — — UDL-2  A2 (10) — — —90 — — UDL-3  A3 (10) — — — 90 — — UDL-4  A4 (10) — — — 90 — — UDL-5  A5(10) — — — 90 — — UDL-6  A6 (10) — — — 90 — — UDL-7  A7 (10) — — — 90 —— UDL-8  A8 (10) — — — 90 — — UDL-9  A9 (10) — — — 90 — — UDL-10 A10(10) — — — 90 — — UDL-11 A11 (10) — — — 90 — — UDL-12 A12 (10) — — — 90— — UDL-13 A13 (10) — — — 90 — — UDL-14 A14 (10) — — — 90 — — UDL-15 A15(10) — — — 90 — — UDL-16 A16 (10) — — — 90 — — UDL-17 A17 (10) — — — 90— — UDL-18 A18 (10) — — — 90 — — UDL-19 A19 (10) — — — 90 — — UDL-20 A20(10) — — — 90 — — UDL-21 A21 (10) — — — 90 — — UDL-22 A22 (10) — — — 90— — UDL-23 A23 (10) — — — 90 — — UDL-24 A24 (10) — — — 90 — — UDL-25 A25(10) — — — 90 — — UDL-26 A26 (10) — — — 90 — — UDL-27 A27 (10) — — — 90— — UDL-28 A28 (10) — — — 90 — — UDL-29  A9 (10) — — S1 80 — — (10)UDL-30  A9 (10) — — S2 80 — — (10) Comparative  R1 (10) — — — 90 — —UDL-1 Comparative  R2 (10) XL1 AG1 — 30 70 — UDL-2 (2) (0.1) Comparative R3 (10) XL1 AG1 — 90 — — UDL-3 (2) (0.1) Comparative  R4 (10) — — — — —90 UDL-4 Comparative  R5 (10) XL1 AG1 — 20 80 — UDL-5 (3) (0.1)

Filling Property Evaluation (Examples 1-1 to 1-30, Comparative Examples1-1 to 1-5)

The compositions (UDL-1 to -30, comparative UDL-1 to -5) for forming anorganic film were each applied onto a SiO₂ wafer substrate having adense hole pattern (hole diameter: 0.16 μm, hole depth: 0.50 μm,distance between the centers of two adjacent holes: 0.32 μm) and bakedusing a hot plate in the atmosphere under the conditions shown in Table7. Thus, a resist underlayer film 8 was formed as shown in FIG. 2 (I).The substrate used was a base substrate 7 (SiO₂ wafer substrate) havinga dense hole pattern as shown in FIG. 2 (G) (top view) and FIG. 2 (H)(sectional view). The sectional shapes of the resulting wafer substrateswere observed with a scanning electron microscope (SEM) to check whetheror not the holes were filled with the organic film without voids(space). Table 7 shows the results. If an organic film material havingpoor filling property is used, voids occur inside the holes in thisevaluation. When an organic film material having good filling propertyis used, the holes are filled with the organic film without voids inthis evaluation as shown in FIG. 2 (I).

TABLE 7 Composition Presence/ for forming absence Baking organic film ofvoids conditions Example 1-1 UDL-1 Absent 300° C. × 60 s Example 1-2UDL-2 Absent 300° C. × 60 s Example 1-3 UDL-3 Absent 250° C. × 60 sExample 1-4 UDL-4 Absent 250° C. × 60 s Example 1-5 UDL-5 Absent 300° C.× 60 s Example 1-6 UDL-6 Absent 300° C. × 60 s Example 1-7 UDL-7 Absent300° C. × 60 s Example 1-8 UDL-8 Absent 250° C. × 60 s Example 1-9 UDL-9Absent 250° C. × 60 s Example 1-10 UDL-10 Absent 300° C. × 60 s Example1-11 UDL-11 Absent 250° C. × 60 s Example 1-12 UDL-12 Absent 300° C. ×60 s Example 1-13 UDL-13 Absent 300° C. × 60 s Example 1-14 UDL-14Absent 250° C. × 60 s Example 1-15 UDL-15 Absent 250° C. × 60 s Example1-16 UDL-16 Absent 250° C. × 60 s Example 1-17 UDL-17 Absent 300° C. ×60 s Example 1-18 UDL-18 Absent 300° C. × 60 s Example 1-19 UDL-19Absent 250° C. × 60 s Example 1-20 UDL-20 Absent 300° C. × 60 s Example1-21 UDL-21 Absent 300° C. × 60 s Example 1-22 UDL-22 Absent 300° C. ×60 s Example 1-23 UDL-23 Absent 250° C. × 60 s Example 1-24 UDL-24Absent 250° C. × 60 s Example 1-25 UDL-25 Absent 250° C. × 60 s Example1-26 UDL-26 Absent 250° C. × 60 s Example 1-27 UDL-27 Absent 250° C. ×60 s Example 1-28 UDL-28 Absent 250° C. × 60 s Example 1-29 UDL-29Absent 250° C. × 60 s Example 1-30 UDL-30 Absent 250° C. × 60 sComparative Comparative Delamination 250° C. × 60 s Example 1-1 UDL-1Comparative Comparative Delamination 250° C. × 60 s Example 1-2 UDL-2Comparative Comparative Present 250° C. × 60 s Example 1-3 UDL-3Comparative Comparative Present 350° C. × 60 s Example 1-4 UDL-4Comparative Comparative Present 250° C. × 60 s Example 1-5 UDL-5

As shown in Table 7, in Examples 1-1 to 1-30 where the inventivecompositions for forming an organic film (UDL-1 to -30) were used, itwas possible to fill the hole patterns without voids, confirming thatthe filling property was high. Furthermore, since a structure having twocarbonyl groups has high adhesiveness to a substrate, delamination wasnot observed. On the other hand, in Comparative Examples 1-1 and 1-2,adhesiveness was insufficient, and delamination was observed on thepatterned substrates. Meanwhile, in Comparative Examples 1-3, 1-4, and1-5, delamination due to insufficient adhesiveness was not observed, butvoids were observed due to insufficient filling property.

Planarizing Property Evaluation (Examples 2-1 to 2-30, ComparativeExamples 2-1 to 2-5)

The compositions (UDL-1 to -30, comparative UDL-1 to -5) for forming anorganic film were each applied onto a base substrate 9 (SiO₂ wafersubstrate) having a giant isolated trench pattern (FIG. 3 (J), trenchwidth: 10 μm, trench depth: 0.10 μm) and baked in the atmosphere using ahot plate under the conditions shown in Table 8. Then, a step (delta 10in FIG. 3 (K)) between the trench portion and the non-trench portion ofa resist underlayer film 10 was observed with an atomic force microscope(AFM) NX10 manufactured by Park systems Corp. Table 8 shows the results.In this evaluation, the smaller the step, the better the planarizingproperty. Note that, in this evaluation, a trench pattern having a depthof 0.10 μm was generally planarized using an organic film materialhaving a film thickness of approximately 0.2 μm. This is a severeevaluation condition to evaluate the planarizing property.

TABLE 8 Composition For Forming Baking Organic Film Step (nm) conditionsExample 2-1 UDL-1 30 300° C. × 60 s Example 2-2 UDL-2 25 300° C. × 60 sExample 2-3 UDL-3 15 250° C. × 60 s Example 2-4 UDL-4 15 250° C. × 60 sExample 2-5 UDL-5 35 300° C. × 60 s Example 2-6 UDL-6 30 300° C. × 60 sExample 2-7 UDL-7 30 300° C. × 60 s Example 2-8 UDL-8 20 250° C. × 60 sExample 2-9 UDL-9 20 250° C. × 60 s Example 2-10 UDL-10 25 300° C. × 60s Example 2-11 UDL-11 20 250° C. × 60 s Example 2-12 UDL-12 30 300° C. ×60 s Example 2-13 UDL-13 30 300° C. × 60 s Example 2-14 UDL-14 25 250°C. × 60 s Example 2-15 UDL-15 15 250° C. × 60 s Example 2-16 UDL-16 15250° C. × 60 s Example 2-17 UDL-17 20 300° C. × 60 s Example 2-18 UDL-1820 300° C. × 60 s Example 2-19 UDL-19 10 250° C. × 60 s Example 2-20UDL-20 20 300° C. × 60 s Example 2-21 UDL-21 25 300° C. × 60 s Example2-22 UDL-22 25 300° C. × 60 s Example 2-23 UDL-23 15 250° C. × 60 sExample 2-24 UDL-24 15 250° C. × 60 s Example 2-25 UDL-25 20 250° C. ×60 s Example 2-26 UDL-26 10 250° C. × 60 s Example 2-27 UDL-27 10 250°C. × 60 s Example 2-28 UDL-28 15 250° C. × 60 s Example 2-29 UDL-29 10250° C. × 60 s Example 2-30 UDL-30 10 250° C. × 60 s ComparativeComparative 50 250° C. × 60 s Example 2-1 UDL-1 Comparative Comparative90 250° C. × 60 s Example 2-2 UDL-2 Comparative Comparative 95 250° C. ×60 s Example 2-3 UDL-3 Comparative Comparative 80 350° C. × 60 s Example2-4 UDL-4 Comparative Comparative 90 250° C. × 60 s Example 2-5 UDL-5

As shown in Table 8, in Examples 2-1 to 2-30 where the inventivecompositions (UDL-1 to -30) for forming an organic film were used, theresist underlayer films had smaller steps between the trench portion andthe non-trench portion compared with Comparative Examples 2-1 to 2-5where comparative compositions (comparative UDL-1 to -5) for forming anorganic film were used, confirming that the planarizing property wasexcellent. Furthermore, comparing Examples 2-29 and 2-30 where compound(A9) was used and a high-boiling-point solvent was added with Example2-9 where compound (A9) was used and a high-boiling-point solvent wasnot added, it was confirmed that planarizing property was furtherimproved by adding the high-boiling-point solvent. On the other hand, inComparative Examples 2-2, 2-3, and 2-5 where a crosslinking agent wasneeded, it was confirmed that the steps in the resist underlayer filmbetween the trench portion and the non-trench portion was large, sincefilm shrinking during baking was great.

Adhesiveness Test (Examples 3-1 to 3-30, Comparative Examples 3-1 to3-5)

The compositions (UDL-1 to -30, comparative UDL-1 to -5) for forming anorganic film were each applied onto a SiO₂ wafer substrate and bakedusing a hot plate in the atmosphere under the conditions shown in Table9. Thus, an organic film with a film thickness of 200 nm was formed.This wafer with an organic film was cut into a 1×1 cm square, and analuminum pin with epoxy adhesive was fastened to the cut wafer with adedicated jig. Thereafter, the assembly was heated with an oven at 150°C. for 1 hour to bond the aluminum pin to the substrate. After coolingto room temperature, initial adhesiveness was evaluated based on theresistance force by a thin-film adhesion strength measurement apparatus(Sebastian Five-A).

FIG. 4 shows an explanatory diagram showing an adhesiveness measurementmethod. In FIG. 4, reference number 11 denotes a silicon wafer(substrate), 12 denotes a cured film, 13 denotes an aluminum pin withadhesive, 14 denotes a support, 15 denotes a grip, and 16 denotes atensile direction. The adhesion is an average of 12 measurement points,and a larger value indicates that the organic film has higheradhesiveness with respect to the substrate. The adhesiveness wasevaluated by comparing the obtained values. Table 9 shows the results.

TABLE 9 Composition for forming Adhesion Baking organic film (mN)conditions Example 3-1 UDL-1 370 300° C. × 60 s Example 3-2 UDL-2 400300° C. × 60 s Example 3-3 UDL-3 420 250° C. × 60 s Example 3-4 UDL-4430 250° C. × 60 s Example 3-5 UDL-5 390 300° C. × 60 s Example 3-6UDL-6 390 300° C. × 60 s Example 3-7 UDL-7 400 300° C. × 60 s Example3-8 UDL-8 440 250° C. × 60 s Example 3-9 UDL-9 460 250° C. × 60 sExample 3-10 UDL-10 360 300° C. × 60 s Example 3-11 UDL-11 390 250° C. ×60 s Example 3-12 UDL-12 440 300° C. × 60 s Example 3-13 UDL-13 450 300°C. × 60 s Example 3-14 UDL-14 390 250° C. × 60 s Example 3-15 UDL-15 430250° C. × 60 s Example 3-16 UDL-16 420 250° C. × 60 s Example 3-17UDL-17 400 300° C. × 60 s Example 3-18 UDL-18 420 300° C. × 60 s Example3-19 UDL-19 470 250° C. × 60 s Example 3-20 UDL-20 410 300° C. × 60 sExample 3-21 UDL-21 440 300° C. × 60 s Example 3-22 UDL-22 450 300° C. ×60 s Example 3-23 UDL-23 490 250° C. × 60 s Example 3-24 UDL-24 410 250°C. × 60 s Example 3-25 UDL-25 430 250° C. × 60 s Example 3-26 UDL-26 360250° C. × 60 s Example 3-27 UDL-27 380 250° C. × 60 s Example 3-28UDL-28 380 250° C. × 60 s Example 3-29 UDL-29 390 250° C. × 60 s Example3-30 UDL-30 400 250° C. × 60 s Comparative Comparative 200 250° C. × 60s Example 3-1 UDL-1 Comparative Comparative 240 250° C. × 60 s Example3-2 UDL-2 Comparative Comparative 300 250° C. × 60 s Example 3-3 UDL-3Comparative Comparative 320 350° C. × 60 s Example 3-4 UDL-4 ComparativeComparative 360 250° C. × 60 s Example 3-5 UDL-5

As shown in Table 9, it was confirmed that Examples 3-1 to 3-30 wherethe inventive compositions (UDL-1 to -30) for forming an organic filmwere used, adhesion was more excellent compared with ComparativeExamples 3-1 to 3-5 where comparative compositions (comparative UDL-1 to-5) for forming an organic film were used. It can be seen that, comparedto comparative UDL-1 and -2 where delamination occurred in the fillingproperty evaluation, Examples 3-1 to 3-30 where the inventivecomposition for forming an organic film was used had approximately twiceas much adhesion. Moreover, in Example 3-13, having two carbonyl groupsand an amide group, the adhesion was approximately 1.4 times theadhesion in Comparative Example 3-4, having only an amide group. Thisreveals that having both a structure having two carbonyl groups and anamide group contributes to exhibition of high adhesiveness. Furthermore,Examples 3-21 to 3-23 having a triple bond terminal group haveapproximately 1.2 to 1.3 times the adhesion of Comparative Example 3-5,not having a triple bond terminal group. Thus, it is revealed that thereduction of film shrinking attributable to a triple bond terminal groupcontributes to adhesiveness.

Film Shrinking Test (Examples 4-1 to 4-30, Comparative Examples 4-1 to4-5)

UDL-1 to -30, and comparative UDL-1 to -5 prepared above were eachapplied onto a Bare-Si substrate, baked using a hot plate in theatmosphere at 100° C. for 60 seconds, and the film thickness wasmeasured. Next, additional baking was performed under the bakingconditions described in Table 10 in the atmosphere, and the filmthickness was measured again. The film shrinking rate was evaluated bycalculating the ratio of the film thicknesses before and after theadditional baking. That is, film shrinking rate (%)=100×{(film thicknessbefore additional baking)−(film thickness after additionalbaking)}/(film thickness before additional baking). Table 10 shows theresults.

TABLE 10 Composition Film for forming shrinking Baking organic film rate(%) conditions Example 4-1 UDL-1 3.1 300° C. × 60 s Example 4-2 UDL-22.7 300° C. × 60 s Example 4-3 UDL-3 1.6 250° C. × 60 s Example 4-4UDL-4 1.4 250° C. × 60 s Example 4-5 UDL-5 2.8 300° C. × 60 s Example4-6 UDL-6 2.5 300° C. × 60 s Example 4-7 UDL-7 2.6 300° C. × 60 sExample 4-8 UDL-8 2.2 250° C. × 60 s Example 4-9 UDL-9 2.5 250° C. × 60s Example 4-10 UDL-10 3.1 300° C. × 60 s Example 4-11 UDL-11 1.7 250° C.× 60 s Example 4-12 UDL-12 2.6 300° C. × 60 s Example 4-13 UDL-13 2.5300° C. × 60 s Example 4-14 UDL-14 1.9 250° C. × 60 s Example 4-15UDL-15 1.6 250° C. × 60 s Example 4-16 UDL-16 1.8 250° C. × 60 s Example4-17 UDL-17 2.9 300° C. × 60 s Example 4-18 UDL-18 2.3 300° C. × 60 sExample 4-19 UDL-19 1.8 250° C. × 60 s Example 4-20 UDL-20 2.0 300° C. ×60 s Example 4-21 UDL-21 2.3 300° C. × 60 s Example 4-22 UDL-22 2.5 300°C. × 60 s Example 4-23 UDL-23 1.2 250° C. × 60 s Example 4-24 UDL-24 1.5250° C. × 60 s Example 4-25 UDL-25 1.7 250° C. × 60 s Example 4-26UDL-26 2.9 250° C. × 60 s Example 4-27 UDL-27 2.7 250° C. × 60 s Example4-28 UDL-28 2.8 250° C. × 60 s Example 4-29 UDL-29 6.2 250° C. × 60 sExample 4-30 UDL-30 5.8 250° C. × 60 s Comparative Comparative 2.4 250°C. × 60 s Example 4-1 UDL-1 Comparative Comparative 15.3 250° C. × 60 sExample 4-2 UDL-2 Comparative Comparative 13.8 250° C. × 60 s Example4-3 UDL-3 Comparative Comparative 2.8 350° C. × 60 s Example 4-4 UDL-4Comparative Comparative 12.4 250° C. × 60 s Example 4-5 UDL-5

As shown in Table 10, it was confirmed that the shrinking rate after theadditional baking was low in Examples 4-1 to 4-28 where the inventivecompositions (UDL-1 to -28) for forming an organic film were used. Onthe other hand, in Comparative Examples 4-2, 4-3, and 4-5 wherecompositions (comparative UDL-2, -3, -5) for forming an organic film forthe Comparative Examples were used, the shrinking rate after theadditional baking was high since a crosslinking agent was contained, andfluctuation in the film thickness was large compared to Examples 4-1 to4-28. Meanwhile, in Examples 4-29 and 4-30 where the inventivecompositions (UDL-29, -30) for forming an organic film were used, thefilm shrinking rate after the additional baking was high compared withExample 4-9 where the same compound was used since a high-boiling-pointsolvent is contained and the solvent remains in the film after thebaking at 100° C. However, this was half the film shrinking rate ofComparative Examples 4-2, 4-3, and 4-5 or less. Note that in ComparativeExamples 4-1 and 4-4 where comparative compositions (comparative UDL-1,-4) for forming an organic film were used, the shrinking rate was lowbecause a triple-bond-containing terminal group was contained.

Pattern Etching Test (Examples 5-1 to 5-30, Comparative Examples 5-1 to5-5)

UDL-1 to -30 prepared above and comparative UDL-1 to -5 were eachapplied onto a SiO₂ substrate having a trench pattern (trench width: 10μm, trench depth: 0.10 μm) with a SiO₂ film formed, the SiO₂ film havinga film thickness of 200 nm treated with HMDS. Then, a resist underlayerfilm was formed by baking under the conditions shown in Table 14 in theatmosphere so that the film thickness on the Bare-Si substrate was 200nm. A silicon-atom-containing resist middle layer material (SOG-1) wasapplied onto the resist underlayer film and baked at 220° C. for 60seconds to form a resist middle layer film having a film thickness of 35nm. A resist upper layer film material (SL resist for ArF) was appliedthereon and baked at 105° C. for 60 seconds to form a resist upper layerfilm having a film thickness of 100 nm. A liquid immersion top coat(TC-1) was applied onto the resist upper layer film and baked at 90° C.for 60 seconds to form a top coat having a film thickness of 50 nm.

The resist upper layer film material (monolayer resist for ArF) wasprepared by: dissolving a polymer (RP1), an acid generator (PAG1), and abasic compound (Amine1) into a solvent containing 0.1 mass % FC-430(manufactured by Sumitomo 3M Ltd.) in proportions shown in Table 11; andfiltering the solution through a 0.1-μm filter made of a fluorinatedresin.

TABLE 11 Acid Basic Polymer generator compound Solvent (parts (parts(parts (parts by mass) by mass) by mass) by mass) SL resist for RP1 PAG1Amine1 PGMEA ArF (100) (6.6) (0.8) (2500)

The structural formulae of the polymer (RP1), acid generator (PAG1), andbasic compound (Amine1) used are shown below.

The liquid immersion top coat material (TC-1) was prepared by:dissolving a top coat polymer (PP1) into organic solvents in proportionsshown in Table 12; and filtering the solution through a 0.1-μm filtermade of a fluorinated resin.

TABLE 12 Organic Polymer solvent (parts (parts by mass) by mass) TC-1PP1 Diisoamyl ether (2700) (100) 2-methyl-1-butanol (270)

The structural formula of the used polymer (PP1) is shown below.

The silicon-atom-containing resist middle layer material (SOG-1) wasprepared by: dissolving a polymer shown by an ArF silicon-containingmiddle layer film polymer (SiP1) and a crosslinking catalyst (CAT1) intoan organic solvent containing 0.1 mass % FC-4430 (manufactured bySumitomo 3M Ltd.) in proportions shown in Table 13; and filtering thesolution through a filter made of a fluorinated resin with a pore sizeof 0.1 μm.

TABLE 13 Thermally crosslinking Organic Polymer catalyst solvent (parts(parts (parts by mass) by mass) by mass) SOG-1 SiP1 CAT1 Propyleneglycol monoethyl (100) (1) ether (4000)

The structural formulae of the used ArF silicon-containing middle layerfilm polymer (SiP1) and crosslinking catalyst (CAT1) are shown below.

Next, the resulting substrate was exposed to light with an ArF liquidimmersion exposure apparatus (NSR-S610C manufactured by NikonCorporation, NA: 1.30, σ: 0.98/0.65, 35° s-polarized dipoleillumination, 6% halftone phase shift mask), baked (PEB) at 100° C. for60 seconds, and developed with a 2.38 mass % tetramethylammoniumhydroxide (TMAH) aqueous solution for 30 seconds. Thus, a 55 nm 1:1positive line and space pattern was obtained.

Next, using an etching apparatus Telius manufactured by Tokyo ElectronLimited, the SOG-1 film was processed by dry etching while using theresist upper layer film pattern as an etching mask; the resistunderlayer film was processed while using the SOG-1 film pattern as anetching mask; and the SiO₂ film was processed while using the resistunderlayer film pattern as an etching mask. The etching conditions wereas follows.

Conditions for transferring the resist upper layer film pattern to theSOG-1 film.

Chamber pressure: 10.0 PaRF power: 1,500 WCF₄ gas flow rate: 15 sccmO₂ gas flow rate: 75 sccm

Time: 15 sec

Conditions for transferring the SOG-1 film pattern to the resistunderlayer film.

Chamber pressure: 2.0 PaRF power: 500 WAr gas flow rate: 75 sccmO₂ gas flow rate: 45 sccm

Time: 120 sec

Conditions for transferring the resist underlayer film pattern to theSiO₂ film.

Chamber pressure: 2.0 PaRF power: 2,200 WC₅F₁₂ gas flow rate:C₂F₆ gas flow rate: 10 sccmAr gas flow rate: 300 sccmO₂ gas flow rate: 60 sccm

Time: 90 sec

The pattern cross sections were observed with an electron microscope(S-4700) manufactured by Hitachi, Ltd. Table 14 shows the results.

TABLE 14 Pattern profile Composition after etching for for formingtransferring Baking organic film to substrate conditions Example 5-1UDL-1 Vertical profile 300° C. × 60 s Example 5-2 UDL-2 Vertical profile300° C. × 60 s Example 5-3 UDL-3 Vertical profile 250° C. × 60 s Example5-4 UDL-4 Vertical profile 250° C. × 60 s Example 5-5 UDL-5 Verticalprofile 300° C. × 60 s Example 5-6 UDL-6 Vertical profile 300° C. × 60 sExample 5-7 UDL-7 Vertical profile 300° C. × 60 s Example 5-8 UDL-8Vertical profile 250° C. × 60 s Example 5-9 UDL-9 Vertical profile 250°C. × 60 s Example 5-10 UDL-10 Vertical profile 300° C. × 60 s Example5-11 UDL-11 Vertical profile 250° C. × 60 s Example 5-12 UDL-12 Verticalprofile 300° C. × 60 s Example 5-13 UDL-13 Vertical profile 300° C. × 60s Example 5-14 UDL-14 Vertical profile 250° C. × 60 s Example 5-15UDL-15 Vertical profile 250° C. × 60 s Example 5-16 UDL-16 Verticalprofile 250° C. × 60 s Example 5-17 UDL-17 Vertical profile 300° C. × 60s Example 5-18 UDL-18 Vertical profile 300° C. × 60 s Example 5-19UDL-19 Vertical profile 250° C. × 60 s Example 5-20 UDL-20 Verticalprofile 300° C. × 60 s Example 5-21 UDL-21 Vertical profile 300° C. × 60s Example 5-22 UDL-22 Vertical profile 300° C. × 60 s Example 5-23UDL-23 Vertical profile 250° C. × 60 s Example 5-24 UDL-24 Verticalprofile 250° C. × 60 s Example 5-25 UDL-25 Vertical profile 250° C. × 60s Example 5-26 UDL-26 Vertical profile 250° C. × 60 s Example 5-27UDL-27 Vertical profile 250° C. × 60 s Example 5-28 UDL-28 Verticalprofile 250° C. × 60 s Example 5-29 UDL-29 Vertical profile 250° C. × 60s Example 5-30 UDL-30 Vertical profile 250° C. × 60 s ComparativeComparative Pattern collapse 250° C. × 60 s Example 5-1 UDL-1Comparative Comparative Pattern collapse 250° C. × 60 s Example 5-2UDL-2 Comparative Comparative Pattern collapse 250° C. × 60 s Example5-3 UDL-3 Comparative Comparative Pattern collapse 350° C. × 60 sExample 5-4 UDL-4 Comparative Comparative Pattern collapse 250° C. × 60s Example 5-5 UDL-5

As shown in Table 14, it was confirmed from the results of the inventivematerials (Examples 5-1 to 5-30) for forming an organic film that theresist upper layer film pattern was favorably transferred to the finalsubstrate in each case, and that the inventive materials for forming anorganic film are suitably used in fine processing according to themultilayer resist method. On the other hand, in Comparative Examples 5-1to 5-5, filling property and adhesiveness were insufficient, asdemonstrated in the filling property evaluation and the adhesivenesstest. Therefore, pattern collapse occurred at patterning, and it was notpossible to form a pattern.

Patterning Test (Examples 6-1 to 6-30, Comparative Examples 6-1 to 6-5)

UDL-1 to -30 prepared above and comparative UDL-1 to -5 were eachapplied onto a SiO₂ substrate having a trench pattern (trench width: 10μm, trench depth: 0.10 μm) with a SiO₂ film formed, the SiO₂ film havinga film thickness of 200 nm treated with HMDS. A coating film was formedby the same method as the pattern etching test except that the bakingwas performed under the conditions shown in Table 15 under such anitrogen stream that the oxygen concentration was controlled to 0.2% orless. Then, patterning and dry etching were performed, and the obtainedpattern profile was observed.

TABLE 15 Pattern profile Composition after etching for for formingtransferring to Baking organic film substrate conditions Example 6-1UDL-1 Vertical profile 300° C. × 60 s Example 6-2 UDL-2 Vertical profile300° C. × 60 s Example 6-3 UDL-3 Vertical profile 250° C. × 60 s Example6-4 UDL-4 Vertical profile 250° C. × 60 s Example 6-5 UDL-5 Verticalprofile 300° C. × 60 s Example 6-6 UDL-6 Vertical profile 300° C. × 60 sExample 6-7 UDL-7 Vertical profile 300° C. × 60 s Example 6-8 UDL-8Vertical profile 250° C. × 60 s Example 6-9 UDL-9 Vertical profile 250°C. × 60 s Example 6-10 UDL-10 Vertical profile 300° C. × 60 s Example6-11 UDL-11 Vertical profile 250° C. × 60 s Example 6-12 UDL-12 Verticalprofile 300° C. × 60 s Example 6-13 UDL-13 Vertical profile 300° C. × 60s Example 6-14 UDL-14 Vertical profile 250° C. × 60 s Example 6-15UDL-15 Vertical profile 250° C. × 60 s Example 6-16 UDL-16 Verticalprofile 250° C. × 60 s Example 6-17 UDL-17 Vertical profile 300° C. × 60s Example 6-18 UDL-18 Vertical profile 300° C. × 60 s Example 6-19UDL-19 Vertical profile 250° C. × 60 s Example 6-20 UDL-20 Verticalprofile 300° C. × 60 s Example 6-21 UDL-21 Vertical profile 300° C. × 60s Example 6-22 UDL-22 Vertical profile 300° C. × 60 s Example 6-23UDL-23 Vertical profile 250° C. × 60 s Example 6-24 UDL-24 Verticalprofile 250° C. × 60 s Example 6-25 UDL-25 Vertical profile 250° C. × 60s Example 6-26 UDL-26 Vertical profile 250° C. × 60 s Example 6-27UDL-27 Vertical profile 250° C. × 60 s Example 6-28 UDL-28 Verticalprofile 250° C. × 60 s Example 6-29 UDL-29 Vertical profile 250° C. × 60s Example 6-30 UDL-30 Vertical profile 250° C. × 60 s ComparativeComparative Pattern collapse 250° C. × 60 s Example 6-1 UDL-1Comparative Comparative Pattern collapse 250° C. × 60 s Example 6-2UDL-2 Comparative Comparative Pattern collapse 250° C. × 60 s Example6-3 UDL-3 Comparative Comparative Pattern collapse 350° C. × 60 sExample 6-4 UDL-4 Comparative Comparative Pattern collapse 250° C. × 60s Example 6-5 UDL-5

As shown in Table 15, it was confirmed from the results of the inventivematerials (Examples 6-1 to 6-30) for forming an organic film that theresist upper layer film pattern was favorably transferred to the finalsubstrate, in each case, and that the inventive materials for forming anorganic film are suitably used in fine processing according to themultilayer resist method even when the film is formed in an inert gas.On the other hand, in Comparative Examples 6-1 to 6-5, pattern collapseoccurred as in the case where the film was formed in the atmosphere, andit was not possible to form a pattern.

From the above, it was revealed that the inventive materials for formingan organic film have high filling and planarizing properties andadhesion to a substrate. Thus, the inventive materials for forming anorganic film are extremely useful as materials for forming an organicfilm used in multilayer resist methods. Moreover, the inventivepatterning process using these materials can form a fine pattern withhigh precision even when the body to be processed is a steppedsubstrate.

It should be noted that the present invention is not limited to theabove-described embodiments. The embodiments are just examples, and anyexamples that have substantially the same feature and demonstrate thesame functions and effects as those in the technical concept disclosedin claims of the present invention are included in the technical scopeof the present invention.

1. A material for forming an organic film, comprising: a compound shownby the following general formula (1); and an organic solvent,

wherein in the general formula (1), X represents an organic group with avalency of “n” having 2 to 50 carbon atoms or an oxygen atom, “n”represents an integer of 1 to 10, and R₁ independently represents any ofthe following general formulae (2),

wherein in the general formulae (2), broken lines represent attachmentpoints to X, and Q₁ represents a monovalent organic group containing acarbonyl group, at least a part of which is a group shown by thefollowing general formulae (3),

wherein in the general formulae (3), broken lines represent attachmentpoints, X₁ represents a single bond or a divalent organic group having 1to 20 carbon atoms optionally having a substituent when the organicgroup has an aromatic ring, R₂ represents a hydrogen atom, a methylgroup, an ethyl group, or a phenyl group, and ** represents anattachment point.
 2. The material for forming an organic film accordingto claim 1, wherein the compound of the general formula (1) is any ofthe following general formulae (4), (6), (7), (8), (9), (10), (11),(12), (13), and (14),

wherein in the general formula (4), n7 and n8 each independentlyrepresent 0 or 1, W represents a single bond or any structure shown bythe following general formulae (5), R₁ has the same meaning as definedabove, m1 and m2 each independently represent an integer of 0 to 4, andm1+m2 is 1 or more to 8 or less,

wherein in the general formulae (5), n9 represents an integer of 0 to 3,R_(a) to R_(f) each independently represent a hydrogen atom or anoptionally fluorine-substituted alkyl group having 1 to 10 carbon atomsor phenyl group, and R_(a) and R_(b) are optionally bonded with eachother to form a ring,

wherein in the general formula (6), R_(g) represents a hydrogen atom, amethyl group, or a phenyl group,

wherein in the general formulae (7) to (11), R₁ has the same meaning asdefined above, R_(h), R_(i), R_(j), R_(k), R_(l), R_(m), and R_(n) eachrepresent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2to 10 carbon atoms, or a benzyl group or a phenyl group optionallyhaving a substituent on an aromatic ring, Y represents R₁, a hydrogenatom, an alkyl group having 1 to 10 carbon atoms, an alkynyl grouphaving 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbonatoms, and at least two of the four Ys in the general formula (11)represent R₁,

wherein in the general formulae (12) to (14), R₁ has the same meaning asdefined above, R_(o) in the general formula (12) represents a linearsaturated or unsaturated divalent hydrocarbon group having 1 to 20carbon atoms or a branched or cyclic saturated or unsaturated divalenthydrocarbon group having 3 to 20 carbon atoms, and R_(p) in the generalformula (13) represents a hydrogen atom or an alkyl group having 1 to 10carbon atoms.
 3. The material for forming an organic film according toclaim 1, wherein Q₁ in the general formula (2) comprises any one or moreshown by the general formulae (3) and any one or more shown by thefollowing general formulae (15) and (16),

wherein R_(q) in the general formula (15) represents a linear saturatedor unsaturated hydrocarbon group having 1 to 30 carbon atoms or abranched or cyclic saturated or unsaturated hydrocarbon group having 3to 30 carbon atoms, a methylene group comprised in R_(q) is optionallysubstituted with an oxygen atom or a carbonyl group, and in the generalformula (16), R_(s) represents a hydrogen atom, a linear hydrocarbongroup having 1 to 10 carbon atoms, or a branched hydrocarbon grouphaving 3 to 10 carbon atoms, R_(t) represents a linear hydrocarbon grouphaving 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10carbon atoms, a halogen atom, a nitro group, an amino group, a nitrilegroup, an alkoxycarbonyl group having 1 to 10 carbon atoms, or analkanoyloxy group having 1 to 10 carbon atoms, n11 represents 0 to 2,n12 and n13 represent a number of substituents on the aromatic ring, n12and n13 represent an integer of 0 to 7, and n12+n13 is 0 or more to 7 orless.
 4. The material for forming an organic film according to claim 1,wherein the organic solvent is a mixture of one or more organic solventseach having a boiling point of lower than 180° C. and one or moreorganic solvents each having a boiling point of 180° C. or higher.
 5. Amethod for forming an organic film that functions as an organic flatfilm employed in a semiconductor device manufacturing process, themethod comprising: spin-coating a substrate to be processed with thematerial for forming an organic film according to claim 1; and heatingthe substrate to be processed at a temperature of 100° C. or higher to600° C. or lower for 10 to 600 seconds to form a cured film.
 6. A methodfor forming an organic film that functions as an organic flat filmemployed in a semiconductor device manufacturing process, the methodcomprising: spin-coating a substrate to be processed with the materialfor forming an organic film according to claim 1; and heating thesubstrate to be processed in an atmosphere having an oxygenconcentration of 0.1% or more to 21% or less to form a cured film. 7.The method for forming an organic film according to claim 5, wherein thesubstrate to be processed has a structure or a step with a height of 30nm or more.
 8. The method for forming an organic film according to claim6, wherein the substrate to be processed has a structure or a step witha height of 30 nm or more.
 9. A patterning process comprising: forming aresist underlayer film by using the material for forming an organic filmaccording to claim 1 on a body to be processed; forming a resist middlelayer film by using a resist middle layer film material containing asilicon atom on the resist underlayer film; forming a resist upper layerfilm by using a resist upper layer film material being a photoresistcomposition on the resist middle layer film; forming a circuit patternin the resist upper layer film; transferring the pattern to the resistmiddle layer film by etching while using the resist upper layer filmhaving the formed circuit pattern as an etching mask; transferring thepattern to the resist underlayer film by etching while using the resistmiddle layer film having the transferred circuit pattern as an etchingmask; and further forming the circuit pattern on the body to beprocessed by etching while using the resist underlayer film having thetransferred circuit pattern as an etching mask.
 10. A patterning processcomprising: forming a resist underlayer film by using the material forforming an organic film according to claim 1 on a body to be processed;forming a resist middle layer film by using a resist middle layer filmmaterial containing a silicon atom on the resist underlayer film;forming a BARC (organic antireflective coating) on the resist middlelayer film; forming a resist upper layer film by using a resist upperlayer film material being a photoresist composition on the BARC so thata 4-layered film structure is constructed; forming a circuit pattern inthe resist upper layer film; transferring the pattern to the BARC andthe resist middle layer film by etching while using the resist upperlayer film having the formed circuit pattern as an etching mask;transferring the pattern to the resist underlayer film by etching whileusing the resist middle layer film having the transferred circuitpattern as an etching mask; and further forming the circuit pattern onthe body to be processed by etching while using the resist underlayerfilm having the transferred circuit pattern as an etching mask.
 11. Apatterning process comprising: forming a resist underlayer film by usingthe material for forming an organic film according to claim 1 on a bodyto be processed; forming an inorganic hard mask middle layer filmselected from a silicon oxide film, a silicon nitride film, and asilicon oxynitride film on the resist underlayer film; forming a resistupper layer film by using a resist upper layer film material being aphotoresist composition on the inorganic hard mask middle layer film;forming a circuit pattern in the resist upper layer film; transferringthe pattern to the inorganic hard mask middle layer film by etchingwhile using the resist upper layer film having the formed circuitpattern as an etching mask; transferring the pattern to the resistunderlayer film by etching while using the inorganic hard mask middlelayer film having the transferred circuit pattern as an etching mask;and further forming the circuit pattern on the body to be processed byetching while using the resist underlayer film having the transferredcircuit pattern as an etching mask.
 12. A patterning process comprising:forming a resist underlayer film by using the material for forming anorganic film according to claim 1 on a body to be processed; forming aninorganic hard mask middle layer film selected from a silicon oxidefilm, a silicon nitride film, and a silicon oxynitride film on theresist underlayer film; forming a BARC (organic antireflective coating)on the inorganic hard mask middle layer film; forming a resist upperlayer film by using a resist upper layer film material being aphotoresist composition on the BARC, so that a 4-layered film structureis constructed; forming a circuit pattern in the resist upper layerfilm; transferring the pattern to the BARC and the inorganic hard maskmiddle layer film by etching while using the resist upper layer filmhaving the formed circuit pattern as an etching mask; transferring thepattern to the resist underlayer film by etching while using theinorganic hard mask middle layer film having the transferred circuitpattern as an etching mask; and further forming the circuit pattern onthe body to be processed by etching while using the resist underlayerfilm having the transferred circuit pattern as an etching mask.
 13. Thepatterning process according to claim 11, wherein the inorganic hardmask middle layer film is formed by a CVD method or an ALD method. 14.The patterning process according to claim 12, wherein the inorganic hardmask middle layer film is formed by a CVD method or an ALD method. 15.The patterning process according to claim 9, wherein the patternformation on the resist upper layer film is performed by aphotolithography with a wavelength of 10 nm or more to 300 nm or less, adirect drawing by electron beam, a nanoimprinting, or a combinationthereof.
 16. The patterning process according to claim 9, whereindevelopment in the patterning process is alkaline development ordevelopment with an organic solvent.
 17. The patterning processaccording to claim 9, wherein the body to be processed is asemiconductor device substrate or the semiconductor device substratecoated with any of a metal film, a metal carbide film, a metal oxidefilm, a metal nitride film, a metal oxycarbide film, or a metaloxynitride film.
 18. The patterning process according to claim 9,wherein the body to be processed is metallic silicon, titanium,tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold,aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium,cobalt, manganese, molybdenum, or an alloy thereof.
 19. A compound shownby the following general formula (1),

wherein in the general formula (1), X represents an organic group with avalency of “n” having 2 to 50 carbon atoms or an oxygen atom, “n”represents an integer of 1 to 10, and R₁ independently represents any ofthe following general formulae (2)

wherein in the general formulae (2), broken lines represent attachmentpoints to X, and Q₁ represents a monovalent organic group containing acarbonyl group, at least a part of which is a group shown by thefollowing general formulae (3),

wherein in the general formulae (3), broken lines represent attachmentpoints, X₁ represents a single bond or a divalent organic group having 1to 20 carbon atoms optionally having a substituent when the organicgroup has an aromatic ring, R₂ represents a hydrogen atom, a methylgroup, an ethyl group, or a phenyl group, and ** represents anattachment point.
 20. The compound according to claim 19, wherein thecompound of the general formula (1) is any of the following generalformulae (4), (6), (7), (8), (9), (10), (11), (12), (13), and (14),

wherein in the general formula (4), n7 and n8 each independentlyrepresent 0 or 1, W represents a single bond or any structure shown bythe following general formulae (5), R₁ has the same meaning as definedabove, m1 and m2 each independently represent an integer of 0 to 4, andm1+m2 is 1 or more to 8 or less,

wherein in the general formulae (5), n9 represents an integer of 0 to 3,R_(a) to R_(f) each independently represent a hydrogen atom or anoptionally fluorine-substituted alkyl group having 1 to 10 carbon atomsor phenyl group, and R_(a) and R_(b) are optionally bonded with eachother to form a ring,

wherein in the general formula (6), R_(g) represents a hydrogen atom, amethyl group, or a phenyl group,

wherein in the general formulae (7) to (11), R₁ has the same meaning asdefined above, R_(h), R_(i), R_(j), R_(k), R_(l), R_(m), and R_(n) eachrepresent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2to 10 carbon atoms, or a benzyl group or a phenyl group optionallyhaving a substituent on an aromatic ring, Y represents R₁, a hydrogenatom, an alkyl group having 1 to 10 carbon atoms, an alkynyl grouphaving 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbonatoms, and at least two of the four Ys in the general formula (11)represent R₁,

wherein in the general formulae (12) to (14), R₁ has the same meaning asdefined above, R_(o) in the general formula (12) represents a linearsaturated or unsaturated divalent hydrocarbon group having 1 to 20carbon atoms or a branched or cyclic saturated or unsaturated divalenthydrocarbon group having 3 to 20 carbon atoms, and R_(p) in the generalformula (13) represents a hydrogen atom or an alkyl group having 1 to 10carbon atoms.
 21. The compound according to claim 19, wherein Q₁ in thegeneral formula (2) comprises any one or more shown by the generalformulae (3) and any one or more shown by the following general formulae(15) and (16),

wherein R_(q) in the general formula (15) represents a linear saturatedor unsaturated hydrocarbon group having 1 to 30 carbon atoms or abranched or cyclic saturated or unsaturated hydrocarbon group having 3to 30 carbon atoms, a methylene group comprised in R_(q) is optionallysubstituted with an oxygen atom or a carbonyl group, and in the generalformula (16), R_(s) represents a hydrogen atom, a linear hydrocarbongroup having 1 to 10 carbon atoms, or a branched hydrocarbon grouphaving 3 to 10 carbon atoms, R_(t) represents a linear hydrocarbon grouphaving 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10carbon atoms, a halogen atom, a nitro group, an amino group, a nitrilegroup, an alkoxycarbonyl group having 1 to 10 carbon atoms, or analkanoyloxy group having 1 to 10 carbon atoms, n11 represents 0 to 2,n12 and n13 represent a number of substituents on the aromatic ring, n12and n13 represent an integer of 0 to 7, and n12+n13 is 0 or more to 7 orless.